TW583216B - Polyester continuous production process - Google Patents

Polyester continuous production process Download PDF

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Publication number
TW583216B
TW583216B TW090110023A TW90110023A TW583216B TW 583216 B TW583216 B TW 583216B TW 090110023 A TW090110023 A TW 090110023A TW 90110023 A TW90110023 A TW 90110023A TW 583216 B TW583216 B TW 583216B
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Taiwan
Prior art keywords
transesterification
reaction
distillation
reactor
attached
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TW090110023A
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Chinese (zh)
Inventor
Mikio Nakane
Kentaro Yamaguchi
Fuminori Takenaga
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Teijin Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

This invention provides a process for continuously producing a polyester comprising an aromatic dicarboxylic acid and a lower alkyl ester thereof and an alkylene glycol having 2 to 4 carbon atoms as the main glycol component by recycling part or all of a distillate comprising an alkylene glycol having 2 to 4 carbon atoms recovered from a polycondensation reaction step as the main component as a raw material for the polyester. Low-boiling substances contained in the flush distillates and the distillate is supplied to an ester exchange reaction step or esterification reaction step.

Description

583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（彳） 本發明係有關聚酯之連續製造方法。更詳細者係有關 由縮聚反應步驟回收以芳香族羧酸及碳數2〜4亞院基二 醇做爲主成份之聚酯的二醇成份去除低沸點物後，再行使 用同時連續製造之方法者。 先行技術中，以碳數2〜4亞烷基二醇爲主要二醇成 份之聚酯中，又以聚亞烷基對苯二甲酸酯具有其良好的物 理性、化學性質，因此被廣泛用於各種用途。特別是，纖 維、薄膜、其他成型品中，具有良好強度、彈性率等機械 特性、耐熱性等，因此，被廣泛利用於衣料、輪胎帘子線 等產業用纖維、工程塑料等。 通常，此各種用途所使用之聚亞烷基對苯二甲酸酯係 藉由直接聚合法或酯交換法所製造者。直接聚合法係藉由 酸成份與二醇成份相互直接酯化反應後，形成聚酯前驅物 後再使該聚酯前驅物於常壓或減壓下進行縮聚後所製造之 方法者。另外，酯交換法係使酸成份之低級烷酯等二醇進 行酯交換反應後，形成聚酯前驅物後，再使該聚酯前驅物 於常壓或減壓下進行縮聚後，製造之方法者。 由縮聚反應步驟所餾出之二醇成份通常，以管型熱交 換器、濕式冷凝器進行凝縮後，做爲部份原料回收，再利 用之。一般，餾出之碳數2〜4亞烷基二醇中於酯化反應 步驟中含有其副產物之水，或於酯交換反應步驟時含副產 物之低級烷醇之外，藉由主要縮聚反應中產生之分解反應 ，及其他副反應後，含有副產物各種低沸點物。例如：製 造聚丁烯對苯二甲酸酯時，於縮聚反應所餾出之1 ，4 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ ^ _ (請先閲讀背面之注意事項再填寫本頁) £·583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (彳) The present invention relates to a continuous manufacturing method for polyester. In more detail, it is related to the recovery of the diol component of the polyester containing aromatic carboxylic acid and 2 to 4 carbon atoms as the main component through the polycondensation reaction step. After removing the low-boiling point, it can be continuously manufactured at the same time Method. In the prior art, polyalkylene terephthalate has been widely used in polyesters containing 2 to 4 carbon alkylene glycols as the main diol component, so it is widely used. For various uses. In particular, fibers, films, and other molded products have good mechanical properties such as strength and elastic modulus, heat resistance, etc., and are therefore widely used in industrial fibers such as clothing, tire cords, and engineering plastics. Generally, the polyalkylene terephthalate used for these various applications is produced by a direct polymerization method or a transesterification method. The direct polymerization method is a method in which an acid component and a diol component are directly esterified with each other to form a polyester precursor, and then the polyester precursor is subjected to polycondensation under normal pressure or reduced pressure. In addition, the transesterification method is a method for producing a polyester precursor by subjecting a diol such as a lower alkyl ester of an acid component to a transesterification reaction, and then subjecting the polyester precursor to polycondensation under normal pressure or reduced pressure. By. The diol component distilled from the polycondensation reaction step is usually condensed by a tubular heat exchanger and a wet condenser, and then recovered as part of the raw material, and then used. In general, the distilled carbon number of 2 to 4 alkylene glycols includes water as a by-product in the esterification reaction step, or lower alkanol containing the by-products in the transesterification reaction step. After the decomposition reaction and other side reactions in the reaction, it contains various low-boiling substances as by-products. For example: when manufacturing polybutene terephthalate, 1, 4 distilled from the polycondensation reaction-This paper size applies to China National Standard (CNS) A4 (210X297 mm) _ ^ _ (Please read the back first (Notes on this page, please fill out this page) £ ·

、tT -線 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（2 ) 丁二醇中含有藉由1，4 -丁二醇本身之脫水環化反應產 生之四氫呋喃及水等者。又，於製造聚對苯二甲酸乙二醇 酯時，含有藉由主要縮聚反應中之分解反應後產生之乙醛 、2 —甲基—1 ，3 —二氧雜環戊烷、甲基溶纖劑、1， 4 -二氧陸圜及水等。製造聚丙烯對苯二甲酸酯時，含有 藉由主要縮聚反應中之分解反應所產生之丙烯醛、烯丙醇 、3—乙氧基一1一丙醇及水等。因此，未蒸餾所餾出之 二醇成份直接做爲原料使用時，藉由所含有此等低沸點物 後，使附屬於酯交換反應、酯化反應器之蒸餾塔的蒸餾負 荷增加或變動後，其製造步驟呈不安定化，特別是，含有 水份量太多時，將阻礙反應觸媒之活性，反應率呈不定數 ，生產步驟不安定，最後造成製品品質不均，或最終製品 之色相惡化等問題產生。爲回避該問題點，於再利用前使 二醇成份供於系外之另一蒸餾步驟後再進行精製者宜，惟 此法將因蒸餾塔、貯存塔等設置務必大筆投資設備、經費 龐大，不利經濟面。因此，被提出不需進行餾出二醇成份 之精製，做爲原料再利用後，其步驟仍可安定化之方法者 0 做爲此方法者，於特公昭5 5 — 3 3 7 3 4號公報中 被揭示，製造聚丁烯對苯二甲酸酯時，做爲由縮聚反應步 驟之餾出液者，於縮聚反應步驟中使於0 · 2 7 k P a〜 1〇1 k P a之壓力下所餾出二醇成份不進行蒸餾步驟之 精製，做爲原料進行再利用之方法者。特開平 1 0 - 2 7 9 6 7 7號公報中揭示有於聚酯之直接聚合法 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） q (請先閲讀背面之注意事項再填寫本頁) 『裝· 線一 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（3 ) 中，使酯化反應第2段反應槽所餾出之二醇成份未進行蒸 餾步驟之精製，做爲原料進行再利用之方法者。特開平 〇9 一 1 2 4 7 8 3號公報中被揭示有，製造聚酯時，由 縮聚反應步驟所餾出之二醇成份末進行蒸餾步驟之精製， 追加於直接聚合法之酯化反應槽做爲原料進行再利用之方 法者。惟，上記任一方法其二醇成份均含有使觸媒失活濃 度之水份，因此，做爲酯交換反應或酯化反應之原料被再 利用時，水份接觸觸媒後影響活性，將無法避免步驟之變 動。 特開平0 4 — 6 5 4 2 6號公報中被揭示有，製造聚 酯時，使佔總原料組成中水份含量爲0 · 5重量％以下之 範圍者，餾出二醇成份直接進行再利用之方法。此時，雖 可達成步驟之安定化，而，可供與再利用之二醇成份量極 少，其他大部份餾出二醇成份務必進行精製。因此，必須 備有蒸餾設備等，經濟面上不理想。 特公平7 - 1 0 0 7 3 4號公報中被揭示有聚丁烯對 苯二甲酸酯直接聚合法中，供給由縮聚裝置所含有凝縮物 之四氫呋喃及水之二醇成份於附屬於酯化反應器之蒸餾塔 中之方法做成實施例者’此聚酯之製造雖然由無需備有附 帶新穎蒸餾設備面觀爲有效方法者，惟，同時供與四氫呋 喃以外之低沸點物者’因此造成增加酯交換反應或酯化反 應器與附屬之蒸餾塔的蒸餾負荷。針對此，若來做考量’ 於此方法將無法達成目標之低沸點物濃度。 特開昭5 3 — 1 2 6 0 9 6號公報中被揭示藉由直接 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇'〆297公着） _ 6 _ (請先閲讀背面之注意事項再填寫本頁) 『裝·, TT-line 583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Butanediol contains tetrahydrofuran and water produced by the dehydration cyclization reaction of 1,4-butanediol itself By. In the production of polyethylene terephthalate, it contains acetaldehyde, 2-methyl-1, 3-dioxolane, and methyl solvent produced by the decomposition reaction in the main polycondensation reaction. Fiber agent, 1, 4-dioxolane and water. When polypropylene terephthalate is produced, it contains acrolein, allyl alcohol, 3-ethoxy-l-propanol, and water, which are produced by the decomposition reaction in the main polycondensation reaction. Therefore, when the diol component distilled without distillation is directly used as a raw material, after the low boiling point is contained, the distillation load of the distillation tower attached to the transesterification reaction and esterification reactor is increased or changed. , Its manufacturing steps are unstable, especially when it contains too much water, it will hinder the activity of the reaction catalyst, the reaction rate will be indefinite, the production steps will be unstable, and finally it will cause uneven product quality or the hue of the final product. Problems such as deterioration. In order to avoid this problem, it is advisable that the diol component be supplied to another distillation step outside the system before re-purification before re-use. However, this method will require a large investment in equipment and huge funds due to the installation of the distillation column and storage tower , Adverse economic aspects. Therefore, it has been proposed that there is no need to refine the distillate diol component, and the method whose steps can still be stabilized after reuse as a raw material. 0 As the method, Yu Gongzhao 5 5-3 3 7 3 4 It was disclosed in the bulletin that when producing polybutylene terephthalate, as the distillate from the polycondensation reaction step, the polybutene terephthalate was adjusted to 0 · 2 7 k P a to 1〇1 k P a The diol component distilled under the pressure is not purified by the distillation step, and it is used as a method for recycling the raw materials. Japanese Unexamined Patent Publication No. 10-2 7 9 6 7 7 discloses that the direct polymerization method for polyester is applicable to Chinese paper standard (CNS) A4 size (210X297 mm). Q (Please read the precautions on the back before (Fill in this page) 583216 A7 B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. In the description of the invention (3), the diol component distilled from the reaction tank in the second stage of the esterification reaction was not distilled The purification of the steps is used as a method for reusing raw materials. Japanese Unexamined Patent Publication No. 09-2 1 4 7 8 3 discloses that in the production of polyester, the diol component distilled from the polycondensation reaction step is refined at the end of the distillation step and added to the esterification reaction of the direct polymerization method. The tank is used as a method for recycling raw materials. However, in any of the methods described above, the diol component contains water in a concentration that deactivates the catalyst. Therefore, when the raw materials used for the transesterification reaction or esterification reaction are reused, the water will affect the activity after contacting the catalyst. Changes in steps cannot be avoided. Japanese Unexamined Patent Publication No. 0 4 — 6 5 4 2 6 discloses that when polyester is manufactured, if the water content in the total raw material composition is within a range of 0.5% by weight or less, the diol component is distilled off directly and reprocessed. How to use it. At this time, although the stability of the steps can be achieved, and the amount of diol components available for re-use is very small, most of the other diol components distilled off must be purified. Therefore, distillation equipment and the like must be provided, which is not economical. Japanese Patent Publication No. 7-1 0 0 7 3 discloses that in the direct polymerization method of polybutene terephthalate, a diol component supplying tetrahydrofuran and water, which are condensates contained in a polycondensation device, is attached to the ester. The method in the distillation column of the chemical reactor is made as an example. "Although the production of this polyester does not need to be equipped with a novel distillation device, it is an effective method, but it is also used for low boiling points other than tetrahydrofuran." This causes an increase in the distillation load of the transesterification reaction or the esterification reactor and the attached distillation column. In view of this, if we consider ’this method will not achieve the target low boiling point concentration. Japanese Unexamined Patent Publication No. 5 3 — 1 2 6 0 9 6 is disclosed that the Chinese National Standard (CNS) A4 specification (2 丨 〇'〆297) is applied by directly measuring the paper size. _ 6 _ (Please read the back first (Notes on this page, please fill out this page)

、1T 線一 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 ) 聚合法製造聚對苯二甲酸乙二醇酯中，將酯化反應步驟所 產生之乙二醇成份導入附屬於酯化反應槽之蒸餾塔後，去 除低沸點成份後’做爲原料進行再利用之方法。此方法係 以酯化反應步驟爲對象，針對使縮聚步驟所生成之乙二醇 成份直接進行再利用之方法並未提及。總之，於縮聚步驟 所產生之乙二醇務必於系外以大型蒸餾步驟進行蒸餾精製 ，未必爲經濟之方法者。 特開昭6 0 — 1 6 3 9 1 8號公報中被揭示藉由直接 聚合法製造聚對苯二甲酸乙二醇酯中，以縮聚反應器所產 生之乙二醇成份做爲主體之氣體於濕式冷凝器進行凝縮後 ，將其凝縮液導入附屬於酯化反應槽之蒸餾塔後，去除低 沸點不純物後，做爲原料進行再利用之方法者。此製造聚 對苯二甲酸乙二醇酯之方法雖無需設置新穎蒸餾設備做爲 附帶設備，却增加附屬於酯化反應槽之蒸餾塔的蒸餾負荷 ，結果務必具備大型蒸餾塔設備，經濟面不理想者，況且 ，此方法無法達成目標之低沸點物濃度。 又，特開昭5 5 - 5 6 1 2 0號公報中揭示藉由直接 聚合法製造聚對苯二甲酸乙二醇酯中，混合混化反應步驟 所餾出之乙二醇成份與由縮聚反應步驟所餾出後被回收之 乙二醇成份後，做爲原料進行再利用之方法。此法務使於 另一步驟進行精製處理之乙二醇於附屬於縮聚反應器之濕 式冷凝器中供與大量之做爲循環液者。與其他方法相同’ 務必於另一步驟之蒸餾設備中進行精製，亦無經濟面可言 (請先閲讀背面之注意事項再填寫本頁} ，裝- 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583216 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（5 ) 有鑑於上述各問題，本發明目的爲提供一種於聚合以 芳香族二羧酸或其低級烷酯以及碳數2〜4之亞烷二醇做 爲主成份之二醇成份後，連續製造聚酯之方法時，無需使 由縮聚反應步驟餾出之碳數2〜4亞烷二醇做爲主成份之 二醇使用大型蒸餾裝置進行精製，可直接做爲原料進行再 利用’而不致造成反應步驟之不安定，可取得品質安定之 聚酯，同時可達到設備簡化，經濟面佳之方法者。 本發明更有其他目的及優點，由以下說明可證明。 根據本發明，本發明之該目的及優點特徵係以芳香族 二羧酸做爲主要二羧酸成份，以1種選自乙二醇、1，3 一丙二醇、及1 ，4— 丁二醇所成群中之二醇做爲主要二 醇成份之芳香族聚酯經由酯化或酯交換反應及縮聚反應後 ’進行連續製造者，至少使含有由該縮聚反應之該二醇餾 出液附於急驟蒸餾後去除低沸點物之後，至少部份殘留液 於該酯化或酯交換反應中做爲該二醇之一部份進行循環使 用者，藉由芳香族聚酯之連續製造方法而完成。 〔圖面之簡單說明〕 圖1係代表本發明實施模式之流程圖者。 圖2係代表本發明實施另一模式之流程圖者。 圖3係代表本發明實施再另一模式之流程圖者。 主要元件對照表 1 酯交換反應器 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） β (請先閲讀背面之注意事項再填寫本頁) 『裝· 訂 -線一 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（6 2 3 4 5 6 7 8 9 〇 4 7 〇 4 酯交換反應器附屬蒸餾塔 馬達 配管 配管 配管 配管 配管 配管 配管 急驟蒸餾器 配管 配管 昇溫器 凝縮器 配管 昇溫器 配管 馬達 急驟蒸餾器 凝縮器 配管 配管 配管 昇溫器 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 583216 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（7 ) 〔發明之實施形態〕 以下，針對本發明之實施形態進行說明。 做爲本發明製造對象之芳香族聚酯係以芳香族二羧酸 爲主要二羧酸成份者，主要二醇成份爲乙二醇、1，3-丙二醇、或1 ，4 一丁二醇之聚酯者。 又，本發明製造該芳香族聚酯時做爲對象之反應爲酯 交換反應或酯化反應及之後之縮聚反應者。酯交換反應時 ’芳香族二羧酸成份以原於做爲芳香族二羧酸之低級烷酯 使用之原料者宜，又，酯化反應時以原於做爲遊離芳香族 二酸使用之原料者宜。 做爲本發明所使用之芳香族二羧酸者如：對苯二甲酸 、異苯二甲酸、苯二甲酸、萘二羧酸、二^氧基羧酸、二 苯氧乙烷二羧酸等例者。又，做爲芳香族二羧酸之低級烷 酯者如：對苯二甲酸二甲酯、二甲基異苯二甲酸酯、萘二 羧酸二甲酯等例。 本發明中，構成聚酯之二醇所謂「主要」係指針對總 二醇成份時，該成份爲5 0莫耳％以上者，較佳者爲8〇 旲耳％以上’更佳者爲9 8吴耳％以上者。 做爲碳數2〜4之亞烷二醇者如：乙二醇、1，3 — 丙二醇、或1 ，4 — 丁二醇可使用之。 又’亦可使用比例少者，做爲碳數2〜4亞烷二醇以 外之二醇成份者如：乙二醇（主要二醇爲乙二醇以外時） 、新戊一醇、1，2 -丙二醇、1，3 —丙二醇（主二醇 爲1 ’ 3 —丙二醇以外時）、1，3 — 丁二醇、；[，4 一 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） ----- -10· (請先閲讀背面之注意事項再填寫本頁) ，裝· 、11 -線一 583216 A7 B7 五、發明説明（8 ) 丁二醇（主二醇爲1，4 — 丁二醇以外時）、1，5 -戊 二醇、1 ，6 —己二醇、1 ，2 —環己二甲醇、1 ，3 — 環己二甲醇、1 ，4 —環己二甲醇、二乙二醇、三乙二醇 、聚亞烷二醇、丙二醇等例。此等二醇成份以1種使用者 或2種以上合倂使用者均可。又，碳數2〜4之亞烷二 醇以總二醇成份爲基準，亦可佔1 0 〇莫耳％者。 又，本發明聚酯可共聚如：偏苯三酸、均苯四甲酸、 甘油等三官能以上之多官能化合物或苯甲酸、異氰酸苯酯 等單官能化合物等化合物者。 本發明聚酯之製造係於觸媒存在下進行者。 本發明所使用之觸媒爲公知之反應觸媒者，如：銻化 合物、錳化合物、鈦化合物、錫化合物、鋅化合物、鎂化 合物、鍺化合物等可使用之。針對供與此觸媒之位置，供 給方法者並無特別限定，可因應製造條件進行適當選擇。 又，必要時於本發明反應步驟中直接添加1種或2種 以上之慣用以外之熱塑性樹脂、添加劑、無機塡充劑、有 機塡充劑等或與二醇成份共同加入，最後縮聚反應器之出 側可直接以成型機、擠壓機、混合器等煉入之。另外，亦 可進行顆粒化後，使再熔融後將此等煉入者。 本發明中，含有碳數2〜4亞烷二醇之餾出物或擠出 物所分離之低狒點物例如：使用做爲碳數2〜4亞烷二醇 之乙二醇時，其水、乙醛、2 —甲基一 1 ，3 —二氧雜環 戊烷、甲基溶纖劑或此等化合物以外之沸點以1 6 5 °C以 下者爲主要對象者。使用做爲碳數2〜4亞烷二醇之1， 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） (請先閲讀背面之注意事項再填寫本頁) ，裝· 訂 經濟部智慧財產局員工消費合作社印製 -11 - 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) 3 —丙二醇時，其水、烯丙醇、丙烯醛、3 -乙氧基一 1 -丙醇或此等化合物以外之沸點以1 6 5。(：以下者爲主要 ^寸象者。做爲碳數2〜4亞院二醇以1，4 一丁二醇使用 者，其四氫呋喃、水、或四氫呋喃以外之沸點以1 6 5 °C 以下之化合物爲主要對象者。 以下，針對本發明實施形態，參考圖面同時進行詳細 說明。圖1、圖2、圖3係代表本發明之實施流程圖。圖 中相同號碼代表相同意思者。. 本發明中，如上述，至少使含有由縮聚反應之二醇的 飽出液附於急驟蒸I留後去除低沸點物後，於該酯化或酯交 換反應使至少一部份殘留液做爲該部份二醇進行循環使用 者。 首先，藉由圖1進行說明上記方法。 圖1之1係代表酯交換反應器、2代表酯交換反應器 中所附屬之蒸餾塔者，介著酯交換反應器1與配管7進行 連接。做爲往酯交換反應器1之原料者，由配管5供與對 苯二甲酸二甲酯，而，由配管6供與碳數2〜4之亞烷二 醇及反應觸媒，含有由該酯交換反應器1所餾出之水、其 他分解低沸點物、及碳數2〜4亞烷二醇等之甲醇係由配 管7供於酯交換反應器附屬之蒸餾塔2者。更以於該蒸餾 塔2之塔頂上昇之甲醇做爲主成份之蒸氣係於凝縮器1 6 被凝縮，通過配管1 9後被排出系外。以碳數2〜4亞院 二醇做爲主成份之酯交換反應器附屬之蒸餾塔2之殘留液 係介著馬達3，昇溫機1 5進行循環之外，介著配管1 4 (請先閲讀背面之注意事項再填寫本頁) 『裝· 訂 線一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（10) 做爲部份酯交換反應原料被供與之。1 1爲急驟蒸餾器、 介著配管17連接於真空產生器（未示圖）。含有於縮聚 反應步驟所回收之低沸點物二醇成份通過配管1 〇後，於 昇溫機1 8被昇溫後，供入急驟蒸餾器。於該急驟蒸餾器 1 1分離低沸點物之碳數2〜4亞烷二醇成份係介著馬達 4由配管8轉入酯交換反應器1做爲部份原料再利用之。 又，於急驟蒸餾器1 1被分離之低沸點物係於凝縮器1 3 被凝縮，通過配管1 2後，被排出系外。含有酯交換反應 生成物之雙羥烷基對苯二甲酸酯之低分子量聚合物係介著 配管9後，供入初期縮聚反應器（未圖示）。 本發明方法係使含有由該縮聚反應之該二醇餾出液， 於附於該急驟蒸餾前供於酯交換或酯化反應之實施步驟所 附屬之蒸餾塔後，再使其蒸餾塔殘留液藉由附於該急驟蒸 餾進行實施。 利用以下圖2進行說明此方法。 圖2係使縮聚反應步驟所回收之碳數2〜4亞烷二醇 成份供於酯交換反應器附屬蒸餾塔2後，分離低沸點物之 後供於急驟蒸餾器時所代表之流程者。縮聚反應步驟所餾 出之碳數2〜4亞烷二醇成份與由酯交換反應器1所餾出 之碳數2〜4亞烷二醇成份同時做爲酯交換反應器附屬蒸 餾塔2之殘留液被取出一部份介著馬達3供入急驟蒸餾裝 置1 1。殘留排出液與圖1所示步驟相同介著昇溫機1 5 供入酯交換反應器附屬蒸餾塔2。於該急驟蒸餾器1 1分 離低沸點物之碳數2〜4亞烷二醇成份係介著配管8供入 (請先閱讀背面之注意事項再填寫本頁) 訂 -線一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583216 經濟部智慧財產局員工消費合作社印製 A7 _ B7__五、發明説明（1彳） 酯交換反應器1，再利用之。含有酯交換反應生成物之雙 羥烷對苯二甲酸酯低分子量聚合物係介著配管9供入初期 縮聚反應器（未圖示）。 本發明方法之理想形態係含該縮聚反應之該二醇餾出 液附於第1急驟蒸餾與第2急驟蒸餾所成之急驟蒸餾後’ 將第1急驟蒸餾殘留液於附與第2急驟蒸餾之前供入酯交 換或酯化反應之實施步驟所附屬之蒸餾塔後，此蒸餾塔之 殘留液藉由附於該第2急驟蒸餾進行實施者。 藉由圖3進行說明此方法。 圖3係代表縮聚步驟所回收之碳數2〜4亞烷二醇成 份導入急驟蒸餾器2 1後，再供給於附屬於酯交換反應器 1之蒸餾塔2，更使該蒸餾塔2之殘留排出物供入另一個 急驟蒸餾器1 1時之流程例者。急驟蒸餾器2 1係介著凝 縮器2 2、配管2 4連接於真空產生器（未圖示）。含有 縮聚反應所回收低沸點物之碳數2〜4亞烷二醇成份係通 過配管2 5後，於昇溫器2 6進行昇溫後，供入急驟蒸餾 器2 1者。之後介著馬達20，於昇溫器18再進行昇溫 後，導入酯交換反應器所附屬之蒸餾塔2。此時，供於該 蒸餾塔2之碳數2〜4亞烷二醇成份係於急驟蒸餾器2 1 ，其部份低沸點物已由配管2 3被分離去除之，因此，不 影響酯交換反應器附屬蒸餾塔2之運轉負荷。隨後，與酯 交換反應器1所餾出之碳數2〜4亞烷二醇成份同時被做 爲酯交換反應器附屬蒸餾塔2之殘留排出液取出，介著馬 達3供入急驟蒸餾裝置1 1。殘留排出液與圖1及圖2所 (請先閱讀背面之注意事項再填寫本頁)1. 1T line 583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Polyethylene terephthalate produced by the polymerization method, the ethylene glycol component produced in the esterification reaction step After introducing the distillation tower attached to the esterification reaction tank, the low-boiling point components are removed and reused as raw materials. This method is aimed at the esterification reaction step, and the method of directly reusing the ethylene glycol component generated in the polycondensation step is not mentioned. In short, the ethylene glycol produced in the polycondensation step must be distilled and purified in a large distillation step outside the system, which may not be an economic method. Japanese Unexamined Patent Publication No. 6 0 — 1 6 3 9 1 8 discloses that a polyethylene terephthalate produced by a direct polymerization method is mainly composed of a polyethylene glycol component produced by a polycondensation reactor. After condensing in a wet condenser, the condensate is introduced into a distillation tower attached to an esterification reaction tank, and low-boiling impurities are removed and used as a method for recycling raw materials. Although this method of manufacturing polyethylene terephthalate does not require the installation of a novel distillation device as an auxiliary device, it increases the distillation load of the distillation tower attached to the esterification reaction tank. As a result, it must have large-scale distillation tower equipment, which is not economical. Ideally, besides, this method cannot achieve the target low boiling point concentration. In addition, Japanese Patent Application Laid-Open No. 5 5-5 6 1 2 0 discloses that in the production of polyethylene terephthalate by a direct polymerization method, the ethylene glycol component distilled out in the mixing and mixing reaction step and the polycondensation The ethylene glycol component recovered after distillation in the reaction step is used as a method for reusing raw materials. This law allows a large amount of glycol to be recirculated in the wet condenser attached to the polycondensation reactor, which is refined in another step. Same as other methods' Must be refined in the distillation equipment in another step, and there is no economic aspect (please read the precautions on the back before filling out this page}. ) A4 specification (210X297 mm) 583216 Α7 Β7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) In view of the above problems, the purpose of the present invention is to provide an aromatic dicarboxylic acid or its After the lower alkyl ester and the alkene glycol having 2 to 4 carbons are used as the diol component as the main component, the continuous production method of polyester does not need to have the carbon number of 2 to 4 distilling off from the polycondensation reaction step. The diol as the main component is refined using a large-scale distillation device, which can be directly reused as a raw material without causing instability in the reaction step. A stable quality polyester can be obtained, and at the same time, equipment can be simplified and economical methods can be achieved. The present invention has other objects and advantages, which can be proved by the following description. According to the present invention, the objects and advantages of the present invention are mainly aromatic dicarboxylic acids. For the dicarboxylic acid component, an aromatic polyester with a diol selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol as the main diol component is esterified. Or after the transesterification reaction and polycondensation reaction, the continuous manufacturer shall at least attach the diol distillate containing the polycondensation reaction to the rapid distillation to remove the low-boiling substances, and at least part of the residual liquid will be in the esterification or esterification. In the exchange reaction, as a part of the diol, the user is recycled and completed by the continuous production method of aromatic polyester. [Simplified description of the drawing] Fig. 1 is a flowchart representing the implementation mode of the present invention. Figure 2 represents the flow chart of another mode of implementation of the present invention. Figure 3 represents the flow chart of another mode of implementation of the present invention. Comparison of main components Table 1 Transesterification reactor This paper is applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm) β (Please read the precautions on the back before filling in this page) "Packing and binding-line one 583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (6 2 3 4 5 6 7 8 9 〇4 7 〇4 Distillation tower attached to the transesterification reactor Motor piping piping piping piping piping piping piping rapid distillation piping piping warmer condenser piping warmer piping motor rapid distiller condenser piping piping piping warmer (please read the precautions on the back first) (Please fill in this page again) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 583216 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) [Implementation form of the invention] The following The embodiment of the present invention will be described. As the aromatic polyester produced by the present invention, aromatic dicarboxylic acid is used as the main dicarboxylic acid component, and the main diol components are ethylene glycol and 1,3-propanediol. , Or 1,4-butanediol polyester. In addition, the reaction targeted for the production of the aromatic polyester in the present invention is a transesterification reaction or an esterification reaction and a subsequent polycondensation reaction. In the transesterification reaction, it is preferable that the aromatic dicarboxylic acid component is used as a raw material used as a lower alkyl ester of an aromatic dicarboxylic acid, and the esterified reaction is used as a raw material used as a free aromatic diacid. Anyone should. As the aromatic dicarboxylic acid used in the present invention, such as: terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, di ^ oxycarboxylic acid, diphenoxyethanedicarboxylic acid, etc. Case. Examples of the lower alkyl ester of an aromatic dicarboxylic acid include dimethyl terephthalate, dimethyl isophthalate, and dimethyl naphthalate. In the present invention, the so-called "main" of the diol constituting the polyester refers to the total diol component, which is 50 mole% or more, preferably 80 mole% or more, and more preferably 9 8% of Wuer. As the alkylene glycol having a carbon number of 2 to 4, such as ethylene glycol, 1,3-propanediol, or 1,4-butanediol can be used. Also, those with a small proportion can be used as diol components other than alkylene glycols having 2 to 4 carbon atoms such as ethylene glycol (when the main diol is other than ethylene glycol), neopentyl alcohol, 1, 2-propanediol, 1,3-propanediol (when the main diol is other than 1'3-propanediol), 1,3-butanediol, [, 4 A paper size applies the Chinese National Standard (CNS) A4 specification (210 X297 mm) ----- -10 · (Please read the precautions on the back before filling this page), install ·, 11-line 583216 A7 B7 5. Description of the invention (8) Butanediol (main diol (Except 1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-— Examples include cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, and propylene glycol. These diol components may be used by one user or two or more users. In addition, the alkylene glycol having 2 to 4 carbons may be based on the total diol component and may also occupy 100 mole%. In addition, the polyester of the present invention can be copolymerized with trifunctional or higher-functional polyfunctional compounds such as trimellitic acid, pyromellitic acid, and glycerin, or compounds such as monofunctional compounds such as benzoic acid and phenyl isocyanate. The production of the polyester of the present invention is performed in the presence of a catalyst. The catalyst used in the present invention is a well-known reaction catalyst, for example, antimony compounds, manganese compounds, titanium compounds, tin compounds, zinc compounds, magnesium compounds, germanium compounds, and the like can be used. The supply location of this catalyst is not particularly limited by the supply method, and can be appropriately selected according to the manufacturing conditions. In addition, in the reaction step of the present invention, if necessary, one or two or more thermoplastic resins, additives, inorganic fillers, organic fillers and the like are directly added or co-added with the diol component, and finally the polycondensation reactor The exit side can be directly mixed into the molding machine, extruder, mixer, etc. It is also possible to granulate and re-melt these particles after remelting. In the present invention, a low baboon substance separated from a distillate or an extrudate having 2 to 4 carbon atoms, for example, when using ethylene glycol having 2 to 4 carbon alkylene glycols, its Water, acetaldehyde, 2-methyl-1,3-dioxolane, methyl cellosolve, or other compounds whose boiling points are below 16 ° C are the main targets. It is used as the carbon number of 2 ~ 4 alkylene glycol. This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 × 297 mm) (please read the precautions on the back before filling this page). Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -11-583216 A7 B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) 3-When propylene glycol, its water, allyl alcohol, acrolein, 3 -Ethoxy-l-propanol or other compounds have a boiling point of 165. (: The following are the main ones. As a user with 2 to 4 carbon atoms, 1,4-butanediol, the boiling point of tetrahydrofuran, water, or tetrahydrofuran is 16 5 ° C or less. The compound is the main object. In the following, the embodiment of the present invention will be described in detail with reference to the drawings. Figures 1, 2, and 3 represent the implementation flowchart of the present invention. The same numbers in the figure represent the same meaning .. In the present invention, as described above, at least a saturated solution containing a diol from a polycondensation reaction is attached to the rapid distillation. After the low boiling point is removed, at least a part of the residual liquid is used as the esterification or transesterification reaction. This part of the diol is circulated to users. First, the above method will be described with reference to Fig. 1. Fig. 1 represents the transesterification reactor, and 2 represents the distillation tower attached to the transesterification reactor through the transesterification. The reactor 1 is connected to a pipe 7. As a raw material for the transesterification reactor 1, a pipe 5 is used to supply dimethyl terephthalate, and a pipe 6 is used to supply alkylene 2 having a carbon number of 2 to 4. Alcohol and reaction catalyst, which are distilled by the transesterification reactor 1 The water produced, other decomposed low-boiling materials, and methanol having 2 to 4 carbon atoms are supplied to the distillation column 2 attached to the transesterification reactor through a pipe 7. It is even more so at the top of the distillation column 2. The rising methanol as the main component of the vapor is condensed in the condenser 16 and discharged out of the system after passing through the pipe 19. The distillation is attached to the transesterification reactor with carbon number 2 ~ 4 as the main component Residual liquid in tower 2 is circulated through motor 3 and warmer 15, and piping 1 4 (please read the precautions on the back before filling in this page) Standard (CNS) A4 specification (210X297 mm) -12- 583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (10) It is supplied as part of the transesterification reaction raw material. 1 1 is The flash still is connected to a vacuum generator (not shown) via a pipe 17. The low-boiling point diol component recovered in the polycondensation reaction step passes through the pipe 10, and is heated in a temperature increaser 18 to be fed into Flash distillation. Separate low-boiling substances in the flash distillation. The carbon number of 2 to 4 alkylene glycol is transferred from the pipe 8 to the transesterification reactor 1 as a part of the raw material through the motor 4 and reused as a part of the raw material. In addition, the low boiling point separated in the flash still 11 is The condenser 1 3 is condensed and passed through the pipe 12 and discharged out of the system. The low molecular weight polymer containing the dihydroxyalkyl terephthalate of the transesterification reaction product is supplied to the initial stage through the pipe 9 Polycondensation reactor (not shown). The method of the present invention is a distillation column attached to the implementation step of transesterification or esterification reaction containing the diol distillate from the polycondensation reaction before being attached to the flash distillation. After that, the residual liquid in the distillation column was attached to the flash distillation, and this method was described below with reference to FIG. 2. Fig. 2 is a process representative of a process in which the carbon number of 2 to 4 alkylene glycol recovered in the polycondensation reaction step is supplied to the distillation column 2 attached to the transesterification reactor, and the low-boiling point is separated and then supplied to the flash still. The carbon number 2 ~ 4 alkylene glycol component distilled in the polycondensation reaction step and the carbon number 2 ~ 4 alkylene glycol component distilled from the transesterification reactor 1 are simultaneously used as the distillation column 2 attached to the transesterification reactor. The residual liquid is taken out and partly supplied to the flash distillation device 11 through the motor 3. The residual effluent was supplied to the distillation column 2 attached to the transesterification reactor through a temperature increaser 15 as in the step shown in FIG. 1. In this flash distillation unit, the carbon number of the low-boiling point is 2 to 4 and the alkylene glycol component is supplied through the pipe 8. (Please read the precautions on the back before filling this page.) China National Standard (CNS) A4 specification (210X297 mm) 583216 Printed by A7 _ B7__ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Ester exchange reactor 1 and reuse it. The dihydroxyalkane terephthalate low-molecular-weight polymer containing the product of the transesterification reaction was supplied to the initial polycondensation reactor (not shown) through a pipe 9. The ideal form of the method of the present invention is that the diol distillate containing the polycondensation reaction is attached to the first and second flash distillations, and the first flash distillation residual liquid is attached to the second flash distillation. After previously supplying the distillation column attached to the step of carrying out the transesterification or esterification reaction, the residual liquid of this distillation column is carried out by attaching it to the second flash distillation. This method will be described with reference to FIG. 3. FIG. 3 represents the carbon number of 2 to 4 recovered from the polycondensation step. After the components of the alkylene glycol are introduced into the flash distillation unit 21, they are supplied to the distillation column 2 attached to the transesterification reactor 1, so that the distillation column 2 remains. Example of the flow when the effluent is fed into another flash still 11. The flash still 2 1 is connected to a vacuum generator (not shown) via a condenser 2 2 and a pipe 2 4. The alkylene glycol component having 2 to 4 carbons containing low-boiling matter recovered from the polycondensation reaction is passed through a pipe 25, heated up in a temperature riser 26, and then supplied to a flash still 21. Thereafter, the temperature is raised in the temperature increaser 18 via the motor 20 and then introduced into the distillation column 2 attached to the transesterification reactor. At this time, the carbon number 2 to 4 of the alkylene glycol component supplied to the distillation column 2 is in the flash still 2 1, and a part of low boiling points thereof has been separated and removed by the pipe 2 3. Therefore, the transesterification is not affected. The operating load of the distillation column 2 attached to the reactor. Subsequently, the 2 to 4 carbon distillate components distilled with the transesterification reactor 1 are simultaneously taken out as the residual effluent of the distillation tower 2 attached to the transesterification reactor, and fed into the flash distillation device 1 through the motor 3 1. Residual discharge liquid as shown in Figures 1 and 2 (Please read the precautions on the back before filling this page)

、1T 線一 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -14 - 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（12) 示步驟相同介著昇溫器1 5供入酯交換反應器附屬蒸餾塔 2 °更於該急驟蒸餾器1 1其低沸點物被分離之碳數2〜 4亞烷二醇成份介著配管8供入酯交換反應器1後，進行 再利用。含有酯交換反應生成物之雙羥烷基對苯二甲酸酯 之低分子量聚合物係介著配管9供入初期縮聚反應器（未 圖示）。 如以上所構成之原裝置中利用圖1、圖2及圖3針對 藉由酯交換法連續性製造聚亞烷對苯二甲酸酯之方法進行 詳細說明。 圖1中’首先，原料對苯二甲酸二甲酯、碳數2〜4 亞烷二醇及鈦酸四丁氧金屬供於酯交換反應器1。其中該 碳數2〜4之亞烷二醇與該對苯二甲酸二甲酯相互莫耳比 以1 · 1 ·· 1〜2 · 5 : 1之範圍者宜，特別以1 · 3 ·· 1〜2 · 0 : 1者更爲理想。又，酯交換反應器內之溫度 如：設定於1 5 0〜2 6 0 t，所供給原料於常壓下附與 酯交換反應。其間，以餾出之甲醇做爲主成份之副產蒸氣 係由配管7導入酯交換反應器附屬蒸餾塔2者。酯交換反 應之生成物持續被利往縮聚反應步驟，於反應溫度2 0 0 〜3 0 0 °C，減壓下進行縮聚反應。其中，針對酯交換反 應器及該聚合反應器之數以及反應器之形式並無特別限定 。另外，亦未限定其操作壓力、溫度者，必要時，亦可於 不活性氣體氣分下進行此等反應。更且，最後取得之聚亞 烷對苯二甲酸酯聚合物係於造粒化、必要時更藉由固相聚 合進行高分子量化。 I--------_裝-- (請先閲讀背面之注意事項再填寫本頁) 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（13 ) 以各縮聚反應器所餾出碳數2〜4之亞烷二醇做爲主 成份之副產蒸氣於冷凝縮器被凝縮、凝縮之餾出液經過配 管1 0與昇溫器1 8後送往急驟蒸餾器1 1。又，留出液 中，由於含有固著性飛散物等不純物，因此，供於昇溫器 1. 8之前先去除於金網濾器、離心分離機等之固著性飛散 物者宜。急驟蒸餾器1 1之操作壓力、縮聚反應步驟所回 收之碳數2〜4亞院一> 醇成份供與急驟蒸1留益之供給溫度 係其低沸點物被分離後做爲原料再利用時，只要不使其最 終製品色相惡化、或是否阻礙觸媒活性，抑或不使酯交換 反應檷附屬之蒸餾塔蒸餾步驟，其他步驟出現變動之條件 下，可採用各種條件進行之。其中，由碳數2〜4亞烷二 醇成份所分離之水份量變少時，因阻礙觸媒活性，因此， 做爲主要之亞烷二醇者使用1，3 -丙二醇或1 ，4 一丁 二醇時，採用其水份率爲0 · 5重量％以下之操作壓力及 含1，3 -丙二醇或1，4 — 丁二醇之餾出液供給溫度條 件者宜。又，做爲主成份亞烷二醇者，使用乙二醇時，以 採用其水份率爲0 · 0 5重量％以下之操作壓力及含乙二 醇之該餾出液供給溫度條件者宜。其示例如：真空度1 3 kPa〜67kPa者，供給溫度爲130〜220°C。 又，做爲主要亞烷二醇者，使用乙二醇時，於含乙二 醇之該餾出液中其含2 -甲基一 1，3 —二氧雜環戊烷最 大於5 0重量p pm、含甲基溶纖劑大於1 〇重量p pm 則將使製品聚合物之色相惡化。 含於再利用碳數2〜4之亞院二醇成份中所含水份以 I-------_裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（14 ) 外之低沸點物量增加時，酯交換反應器附屬之蒸餾塔2之 負荷增加，爲因應此，務必大筆設備投資，造成步驟不安 定化等，因此，該急驟蒸餾器中除水份之外，亦分離甲醇 、上述低沸點者宜。 以下，針對圖2進行說明。由各縮聚反應步驟所餾出 之碳數2〜4亞烷二醇做爲主成份副產蒸氣係於冷凝器被 凝縮、凝縮之餾出液經過配管1 0與昇溫器1 8後，供入 酯交換反應器附屬之蒸餾塔2。該蒸餾塔2與酯交換反應 所餾出之碳數2〜4亞烷二醇成份共同做爲部份殘留排出 液被取出後，經過急驟蒸餾器1 1後，供於酯交換反應器 1後，再利用之。其中，只要急驟蒸餾步驟無問題，則在 減少酯交換反應器附屬蒸餾塔2之運轉負荷爲目的下亦可 降低蒸餾鍋之溫度，提昇殘留排出液中低沸點物濃度。 以下，針對圖3進行說明。由各縮聚反應器所餾出碳 數2〜4亞烷二醇做爲主成份副產蒸氣係於冷凝器被凝縮 、凝縮之餾出液介著配管2 5、昇溫器2 6導入急驟蒸餾 器2 1。之後，供於酯交換反應器附屬蒸餾塔2，與酯交 換反應所餾出之碳數2〜4亞烷二醇成份共同做爲一部份 殘留排出液被取出，經過急驟蒸餾器1 1之後，供於酯交 換反應器1 ，再利用之。此時，供於酯交換反應器附屬蒸 餾塔2之碳數2〜4亞烷二醇成份其部份低沸點物於急驟 蒸餾器2 1被分離去除，因此，更可期待比圖2流程中之 酯交換反應器附屬蒸餾塔2之負荷大爲減少，而且，即使 酯交換反應器附屬蒸餾塔2之步驟出現變動增加排出液中 (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 583216 經濟部智慧財產局員工消費合作社印製 A 7 B7五、發明説明（15) 之低沸點物時，亦可藉中急驟蒸餾器1 1吸收其變動，更 可期待安定化之步驟。 利用上述本發明之方法後，使縮聚中所餾出之二醇成 份無需利用系外個別大規模蒸餾裝置進行精製，只要設置 成本低，運轉經費少之小型急驟蒸餾裝置，不致使反應步 驟不安定，可達成削減運轉經費與設備簡化者。 又，取出酯交換反應或酯化反應裝置附屬之蒸餾塔殘 留排出液後，於急驟蒸餾裝置藉由蒸餾後可減少酯交換反 應或酯化反應裝置附屬蒸餾塔之負荷、削減酯交換反應或 酯化反應裝置附屬蒸餾塔之運轉經費、可減少整體裝置之 運轉經費。 又，於急驟蒸餾裝置藉由蒸餾後，可簡易控制碳數2 〜4亞烷二醇水份含率爲必要値以下，即使做爲原料再利 用仍不會造成反應步驟之不安定化，可達成削減運轉經費 與設備簡化者。 〔實施例〕 以下，利用圖1、圖2及圖3之流程進行本發明實施 例之具體說明。 首先，針對採用1，4 — 丁二醇做爲碳數2〜4之亞 烷二醇時進行說明。 〔實施例1〕 圖1中，使由配管5之37kg/h對苯二甲酸二甲 (請先閲讀背面之注意事項再填寫本頁) £- 訂 -線一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -18-、 1T line One paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -14-583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) The steps shown are the same with the temperature rising Reactor 1 5 is supplied to the transesterification reactor attached distillation column 2 ° more than the flash distillation unit 1 1 The low-boiling point carbon number is 2 to 4 The alkylene glycol component is fed to the transesterification reactor 1 through a pipe 8 Then, reuse it. A low-molecular-weight polymer containing a dihydroxyalkyl terephthalate product of a transesterification reaction is supplied to an initial polycondensation reactor (not shown) through a pipe 9. In the original device constructed as described above, a method for continuously producing a polyalkylene terephthalate by a transesterification method will be described in detail using Figs. 1, 2, and 3. In FIG. 1 ', first, dimethyl terephthalate, a carbon number of 2 to 4 and an alkylene glycol and metal tetrabutoxide are supplied to the transesterification reactor 1. Wherein, the molar ratio of the alkylene glycol having 2 to 4 carbon atoms and the dimethyl terephthalate to each other is in the range of 1 · 1 · · 1 to 2 · 5: 1, and particularly 1 · 3 · · 1 to 2 · 0: 1 is more desirable. In addition, if the temperature in the transesterification reactor is set to 150 to 260 t, the supplied raw materials are attached to the transesterification reaction under normal pressure. Meanwhile, the by-product steam containing distilled methanol as a main component was introduced into the distillation column 2 attached to the transesterification reactor through a pipe 7. The product of the transesterification reaction is continuously used to the polycondensation reaction step, and the polycondensation reaction is performed at a reaction temperature of 200 to 300 ° C under reduced pressure. Among them, there is no particular limitation on the number of transesterification reactors and the polymerization reactor, and the form of the reactor. In addition, the operating pressure and temperature are not limited, and if necessary, these reactions can be performed under inert gas. Furthermore, the final poly (ethylene terephthalate) polymer obtained was granulated, and if necessary, polymerized by solid-phase polymerization. I --------_ Installation-(Please read the precautions on the back before filling this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) 583216 A7 B7 Ministry of Economic Affairs Printed by the Consumers' Cooperative of the Property Bureau V. Description of the invention (13) The by-product steam with 2 to 4 carbon atoms distilled from each polycondensation reactor as the main component is condensed and condensed. The effluent is sent to the flash still 11 after passing through the piping 10 and the warmer 18. In addition, since the residue contains impurities such as fixed scatterings, it is suitable to remove the fixed scatterings from the gold mesh filter, centrifugal separator, etc. before supplying it to the heater 1.8. The operating pressure of the flash distillator 11 and the number of carbons recovered in the polycondensation reaction step 2 ~ 4. A > The temperature at which the alcohol component is supplied to the flash steam 1 and the benefit is the low boiling point is separated and reused as raw material. In this case, as long as the hue of the final product is not deteriorated, or whether the catalyst activity is hindered, or the transesterification reaction is not performed, the distillation step attached to the distillation column, and other steps may be carried out under various conditions. Among them, when the amount of water separated by the carbon number of 2 to 4 alkylene glycol components is reduced, the catalyst activity is hindered. Therefore, as the main alkylene glycol, 1,3-propanediol or 1,4- In the case of butanediol, an operating pressure with a moisture content of 0.5% by weight or less and a distillate containing 1,3-propanediol or 1,4-butanediol should be used at a temperature condition. In addition, as the main component of alkylene glycol, when using ethylene glycol, it is advisable to use an operating pressure with a moisture content of 0. 05% by weight or less and the temperature of the distillate containing ethylene glycol. . Examples are: those with a vacuum of 1 kPa to 67 kPa and a supply temperature of 130 to 220 ° C. Also, as the main alkylene glycol, when ethylene glycol is used, the distillate containing ethylene glycol contains 2-methyl-1,3-dioxolane at a maximum of 50 weight. p pm, methyl cellosolve greater than 10 weight p pm will worsen the hue of the product polymer. The water content contained in the recycled diol content of the Asian Academy 2 to 4 is I -------_ installed-(Please read the precautions on the back before filling this page) Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -16- 583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (14) When the amount of low-boiling materials outside increases, the transesterification reactor The load of the attached distillation column 2 is increased. In order to respond to this, a large investment in equipment is necessary, causing unstable steps, etc. Therefore, in addition to water, the flash distillation unit also separates methanol and the above-mentioned low boiling point. Hereinafter, FIG. 2 will be described. The 2 to 4 carbons distilled from each polycondensation reaction step are used as the main component, and the by-product vapor is condensed in the condenser. The condensed distillate passes through the piping 10 and the temperature riser 18 and is fed into Distillation column 2 attached to the transesterification reactor. The distillation column 2 and the carbon number 2 to 4 distilled from the transesterification reaction are taken out as a part of the residual exhaust liquid, and then passed through the flash still 11 and then supplied to the transesterification reactor 1. And reuse it. Among them, as long as there is no problem in the rapid distillation step, the temperature of the distillation pot can be lowered for the purpose of reducing the operating load of the distillation column 2 attached to the transesterification reactor, and the concentration of low-boiling substances in the residual effluent can be increased. Hereinafter, FIG. 3 will be described. The 2 to 4 carbons distilled from each polycondensation reactor are used as the main component, and the by-product steam is condensed and condensed in the condenser. The distillate is introduced into the rapid distillation device through the pipe 2 and the temperature riser 26. twenty one. After that, it is supplied to the distillation column 2 attached to the transesterification reactor, and it is taken out as a part of the residual effluent with the carbon number of 2 to 4 distilled from the transesterification reaction. After passing through the flash still 11 For the transesterification reactor 1 and reuse it. At this time, the carbon number 2 to 4 of the alkylene glycol component supplied to the distillation column 2 attached to the transesterification reactor and some of the low-boiling substances are separated and removed in the flash still 21, so it can be expected more than in the flow of FIG. 2 The load on the distillation tower 2 attached to the transesterification reactor is greatly reduced, and even if the steps of the distillation tower 2 attached to the transesterification reactor are changed, the discharge liquid is increased (please read the precautions on the back before filling this page). This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -17-583216 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A 7 B7 V. Low boiling point of invention description (15), you can also borrow The medium and rapid distiller 11 absorbs the change, and can expect a stabilization step. After the method of the present invention is used, the diol component distilled out in the polycondensation does not need to be refined by an external large-scale distillation device. As long as a small-scale flash distillation device with a low cost and a small operating cost is installed, the reaction step is not disturbed , Can achieve reduction of operating expenses and equipment simplification. In addition, after the residual effluent of the distillation column attached to the transesterification reaction or esterification reaction device is taken out, the load on the transesterification reaction or the distillation column attached to the esterification reaction device can be reduced after distillation in the rapid distillation device, and the transesterification reaction or ester can be reduced. The operating expenses of the distillation tower attached to the chemical reaction device can reduce the operating expenses of the overall device. In addition, after the distillation in the rapid distillation device, the carbon content of 2 to 4 carbon atoms can be easily controlled. The water content of the alkylene glycol is required to be less than or equal to 値. Even if it is reused as a raw material, it does not cause instability in the reaction step. Reached to reduce operating expenses and simplify equipment. [Embodiment] Hereinafter, a specific description of an embodiment of the present invention will be described by using the flowcharts of Figs. 1, 2 and 3. First, a case where 1,4-butanediol is used as the alkylene glycol having 2 to 4 carbon atoms will be described. [Example 1] In Figure 1, the 37kg / h dimethyl terephthalate by pipe 5 (please read the precautions on the back before filling this page) £-order-line a paper size applies Chinese national standards ( CNS) A4 size (210X 297 mm) -18-

SZ32W 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（16 ) 酯與由配管6之24kg/h r 1，4 — 丁二醇以及 〇 · 0 3 k g / h r之鈦酸丁氧金屬連續供入酯交換反應 器1 ，於溫度160〜190。(：，常壓下，進行酯交換反 應，餾出理論量8 5 %甲醇後，取得含有雙羥丁基對苯二 甲酸酯之低分子量聚合物。再使所取得之含雙羥丁基對苯 二甲酸酯低分子量聚合物介著配管9後，連續供入初期縮 聚反應器，於溫度230 °C，真空度4 · OkPa下進行 縮聚反應後，取得聚丁烯對苯二甲酸酯低聚物。再將取得 低聚合物連續供入最後縮聚反應器，於溫度2 4 7〜 2 4 8 °C，真空度0 · 2 k P a下進行縮聚反應。所取得 聚丁烯對苯二甲酸酯聚合物之固有黏度（鄰氯苯酚中， 3 5 t下所測定之溶液粘度所算出之値）爲6 2者，此藉 由齒輪泵取出後，於造粒化步驟中進行顆粒化。 又，初期縮聚反應器與最終縮聚反應器之四氫呋喃含 1 · 6重量％，含12重量％甲醇、及〇 · 7重量％水之 1，4 一丁二醇餾出液以7 k g / h於昇溫器1 8昇溫至 150 t：後，介著配管10供入急驟蒸觀器11 °又’急 驟蒸餾器1 1之操作壓力調整爲2 7 k P a °於急驟蒸貪留 器1 1分離低沸點物後之1，4 一 丁二醇成份含〇 · 2重 量％之四氫呋喃、2重量％甲醇、及0·3重量％水者。 將此1，4 — 丁二醇成份6 k g / h r介著配管8供於酯 交換反應器1，做成部份啓始原料之二醇進行再利用。另 外，此時，由配管6之1，4 一丁二醇供給量減至1 8 ‘ k g / h r 者。 本紙張尺度適用中國國家標準（CNS ) A4規格（2i〇 x 297公着） -19- (請先閲讀背面之注意事項再填寫本頁)SZ32W Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (16) Ester and 24kg / hr 1,4-butanediol and 0.03 kg / hr of metal butoxide in pipe 6 Continuously fed into the transesterification reactor 1 at a temperature of 160-190. (: Under normal pressure, a transesterification reaction is carried out, and after distillation of 85.5% of the theoretical amount of methanol, a low molecular weight polymer containing bishydroxybutyl terephthalate is obtained. The obtained bishydroxybutyl containing The terephthalic acid low molecular weight polymer was continuously fed into the initial polycondensation reactor through the pipe 9. After polycondensation reaction was performed at a temperature of 230 ° C and a vacuum of 4 · OkPa, polybutene terephthalic acid was obtained. Ester oligomer. The obtained oligomer is continuously fed into the final polycondensation reactor, and the polycondensation reaction is carried out at a temperature of 2 4 7 to 2 48 ° C and a vacuum of 0 · 2 k Pa. The obtained polybutene pair The inherent viscosity of the phthalic acid ester polymer (calculated from the viscosity of the solution measured at 3 5 t in o-chlorophenol) is 62. This is taken out by a gear pump and then carried out in the granulation step. In addition, the tetrahydrofuran in the initial polycondensation reactor and the final polycondensation reactor contained 1.6% by weight, 12% by weight methanol, and 0.7% by weight 1,4-butanediol distillate at 7 kg. / h in the temperature riser 1 8 to 150 t: After that, it is fed into the flash steam viewer 11 ° through the pipe 10 'again. The operating pressure of the flash distiller 11 was adjusted to 27 kPa. At the flash steam retentator 11, the 1,4-butanediol component contained 0.2% by weight of tetrahydrofuran and 2% by weight. Methanol and 0.3% by weight of water. This 1,4-butanediol component 6 kg / hr is supplied to the transesterification reactor 1 through a pipe 8 to make part of the starting diol for reuse. In addition, at this time, the supply of 1,4-butanediol from piping 6 is reduced to 18 'kg / hr. This paper size applies the Chinese National Standard (CNS) A4 specification (2i0x 297)- 19- (Please read the notes on the back before filling this page)

583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（17 ) 〔實施例2〕 圖2中，使由配管5爲3 7 k g/h r之對苯二甲酸 二甲酯、與由配管6爲24kg/hr之1 ，4 一 丁二醇 、以及0 · 0 3 k g / h r之鈦酸四丁氧金屬連續供入酯 交換反應器1，於溫度160〜190 °C，常壓下，進行 酯交換反應，餾出理論量之8 5 %甲醇後，取得含有雙羥 丁基對苯二甲酸酯之低分子量聚合物。再使取得含此雙羥 丁基對苯二甲酸酯之低分子量聚合物介著配管9連續供入 初期縮聚反應器，於溫度230°C，真空度4 · OkPa 下進行縮聚反應後，取得聚丁烯對苯二甲酸酯低聚合物。 再將取得低聚物連續供於最終縮聚反應器後，於溫度 247〜248°C，真空度0 · 2kPa下進行縮聚反應 。所取得聚丁烯對苯二甲酸酯聚合物之固有粘度（鄰氯苯 酚中，3 5 °C下所測定之溶液粘度算出之値）爲〇 · 6 2 者，此藉由齒輪泵取出後，於造粒化步驟進行顆粒化。 又，將1 · 6重量％之初期縮聚反應器及最終縮聚反 應器之四氫呋喃，含有1 2重量％甲醇、〇 · 7重量％之 水之1，4 一丁二醇餾出液以7 k g / h r於昇溫器1 8 進行昇溫至1 5 0 °C後，介著配管1 0供入酯交換反應器 附屬蒸餾塔2。合倂由酯交換反應器1往酯交換反應器附 屬蒸餾塔2黯出之4 k g / h I* 1，4 — 丁二醇成份後 ，使合計1 1 k g / h r於1 5 0 °C下供入急驟蒸飽器 1 1中。另外，急驟蒸餾器1 1之操作壓力調整爲2 7 k P a。於急驟蒸餾器1 1下分離低沸點後之1 ’ 4 一丁 ----------$-- (請先閲讀背面之注意事項再填寫本頁) 、τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 20- 583216 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（18) 二醇成份含有Ο · 1重量％以下之四氫咲喃、及Ο · 1重 量％以下之甲醇、以及0 · 2重量％之水。此1 ，4 一丁 二醇成份介著配管8以1 0 k g / h r供入酯交換反應器 1後，做爲部份啓始原料之二醇後，再利用之。又，此時 ，由配管6之1，4 一 丁二醇供給量減少爲1 8 k g / hr 〇 〔實施例3〕 圖3中，將3 7kg/h r由配管5之對苯二甲酸二 甲酯、與24kg/hr由配管6之1 ，4 一 丁二醇、以 及0 · 0 3 k g / h r之鈦酸四丁氧金屬連續供入酯交換 反應器1後，於溫度1 6 0〜1 9 0 °C，常壓下進行酯交 換反應後，餾出理論量之8 5 %甲醇後，取得含有雙羥丁 基對苯二甲酸酯之低分子量聚合物。再將含有此雙羥丁基 對苯二甲酸酯之低分子量聚合物介著配管9連續供入初期 縮聚反應器，於溫度23CTC，真空度4 . OkPa下進 行縮聚反應後，取得聚丁烯對對二甲酸酯低聚物。再使該 低聚物連續供入最終縮聚反應器，於溫度2 4 7〜2 4 8 。(：，真空度0 · 2 k P a下進行縮聚反應。所取得聚丁烯 對苯二甲酸酯聚合物之固有粘度（鄰氯苯酚中3 5 °C下所 測定之溶液粘度算出値）爲0 · 6 2者，此藉由齒輪泵取 出後，於造粒化步驟進行顆粒化。 又，含有1 · 6重量％之初期縮聚反應器及最終縮聚 反應器之四氫呋喃、12重量％之甲醇、0.7重纛％之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 (請先閱讀背面之注意事項再填寫本頁) _裝·583216 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (17) [Example 2] In Figure 2, the piping 5 is 3 7 kg / hr of dimethyl terephthalate, and The piping 6 is continuously fed into the transesterification reactor 1 with 1,4-monobutylene glycol at 24 kg / hr and tetrabutoxy metal titanate at 0.3 kg / hr at a temperature of 160 to 190 ° C at normal pressure. After the transesterification reaction, 85% of the theoretical amount of methanol was distilled off, and a low molecular weight polymer containing bishydroxybutyl terephthalate was obtained. The low molecular weight polymer containing the bishydroxybutyl terephthalate was continuously fed into the initial polycondensation reactor through a pipe 9 and subjected to a polycondensation reaction at a temperature of 230 ° C and a vacuum of 4 · OkPa. Polybutene terephthalate oligomer. After the obtained oligomer is continuously supplied to the final polycondensation reactor, the polycondensation reaction is performed at a temperature of 247 to 248 ° C and a vacuum degree of 0 · 2 kPa. The intrinsic viscosity of the obtained polybutene terephthalate polymer (the calculated viscosity of the solution measured at 35 ° C in o-chlorophenol) is 0.62, which is taken out by a gear pump In the granulation step, granulation is performed. In addition, 1.6% by weight of the initial polycondensation reactor and the final polycondensation reactor of tetrahydrofuran contained 1.2% by weight of methanol and 0.7% by weight of 1,4-butanediol distillate at 7 kg / After the temperature was raised to 150 ° C. in the temperature increaser 18, hr was supplied to the distillation column 2 attached to the transesterification reactor through the pipe 10. After combining the 4 kg / h I * 1, 4 —butanediol component from the transesterification reactor 1 to the distillation tower 2 attached to the transesterification reactor, make the total 1 1 kg / hr at 150 ° C Feed into the flash steamer 1 1. In addition, the operating pressure of the flash still 11 was adjusted to 27 kPa. 1 '4 one small after separation of low boiling point in the rapid distillation unit 1 1 ---------- $-(Please read the notes on the back before filling this page), τ This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 20- 583216 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18) The diol component contains tetrahydrofuran in an amount of 0. 1% by weight or less , And 0. 1% by weight of methanol, and 0. 2% by weight of water. The 1,4-butanediol component is supplied to the transesterification reactor 1 at a rate of 10 kg / hr through the pipe 8, and then used as a part of the starting diol. At this time, the 1,4-butanediol supply amount from the pipe 6 was reduced to 18 kg / hr. [Example 3] In FIG. 3, 37 kg / hr was transferred from the dimethyl terephthalate of the pipe 5. Ester and 24 kg / hr were continuously fed into the transesterification reactor 1 through pipe 1-4, butanediol, and 0.03 kg / hr of tetrabutyl oxytitanate at a temperature of 16 0 to 1 After carrying out the transesterification reaction at 90 ° C under normal pressure, distilling off 85% of the theoretical amount of methanol, a low molecular weight polymer containing bishydroxybutyl terephthalate was obtained. The low-molecular-weight polymer containing the dihydroxybutyl terephthalate was continuously fed into the initial polycondensation reactor through a pipe 9 and subjected to a polycondensation reaction at a temperature of 23 CTC and a vacuum of 4. OkPa to obtain polybutene. For paraformate oligomers. The oligomer was continuously fed into a final polycondensation reactor at a temperature of 2 4 7 to 2 4 8. (: The polycondensation reaction is carried out at a vacuum of 0 · 2 k Pa. The inherent viscosity of the obtained polybutene terephthalate polymer (calculation of the solution viscosity at 35 ° C in o-chlorophenol 値) If it is 0.62, this is taken out by a gear pump, and then granulated in a granulation step. In addition, tetrahydrofuran containing 12% by weight of the initial polycondensation reactor and final polycondensation reactor, and 12% by weight of methanol The paper size of 0.7% by weight is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1. (Please read the precautions on the back before filling this page) _Package ·

、1T 線一 583216 A7 _ B7 經濟部智慧財產局員工消費合作杜印製 五、發明説明（19) 水的1，4 一丁二醇餾出液以7 k g / h r ，於昇溫器 2 6昇溫至1 5 0 °C後，介著配管2 5供入急驟蒸餾器 21。又，急驟蒸餾器21之操作壓力調整爲27kPa 者。於急驟蒸餾器2 1分離低沸點物後之1，4 一 丁二醇 成份含有0 · 2重量％之四氫呋喃、2重量％之甲醇、及 0 · 3重量％之水者。再將此1，4 一丁二醇成份於昇溫 器再昇溫至1 5 0 °C後，介著配管1 0供入酯交換反應器 附屬蒸餾塔2。合倂由酯交換反應器1往蒸餾塔2餾出之 1，4 — 丁二醇成份4 k g / h r後，總計1 1 k g / h r於1 5 0 t下供入急驟蒸餾器1 1。又，急驟蒸餾器 1 1之操作壓力調爲2 7 k P a者。於急驟蒸餾器1 1分 離低沸點物後之1 ，4 一丁二醇成份爲含Ο · 1重量％以 下之四氫呋喃、0·1重量％以下之甲醇及0·1重量％ 之水。將此1，4 一 丁二醇成份以1 0 k g / h r介著配 管8供入酯交換反應器1後，做成部份啓發原料之二醇， 再利用之。又，此時，由配管6之1，4 一 丁二醇供給量 爲減至18kg/hr者。 以上實施例所述之聚丁烯對苯二甲酸酯的連續製造方 法中，含有縮聚反應步驟所產生之低沸點物二醇成份無需 於系外個別利用大型蒸餾裝置進行精製，做爲部份原料考 即使再利用乃不致阻礙觸媒活性，可安定生產之。 以下，針對做爲碳數2〜4之亞烷二醇者以採用乙= 醇時進行說明。又，實施例中之色調係於焊接型彩色機器 (日本電色工業公司製Σ 8 0 )經測定後求出L、b値。 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 77 ^ (請先閲讀背面之注意事項再填寫本頁) _裝· 、11 線 5832l6 Α7 、^----- Β7 __ 五、發明説明（2〇) L値代表明亮、L値愈高代表亮色相聚合物者。b値代表 黃色〜青色、b値愈低，代表汎黃色較少之色相聚合物者 〇 〔實施例4〕 圖1中，將3 7 k g/h r由配管5之對苯二甲酸二 甲酯、與21kg/hr由配管6之乙二醇以及〇·01 k g / h r之醋酸錳四水鹽連續供入酯交換反應器1後， 於溫度2 0 0〜2 4 0 t，常壓下進行酯交換反應，餾出 甲醇後取得含有雙羥乙基對苯二甲酸酯之低分子量聚合物 。再將該含雙羥乙基對苯二甲酸酯之低分子量聚合物介著 配管9連續供入初期縮聚反應器，加入0 · 0 2 k g / h r之三氧化銻後，於溫度2 9 0 °C，真空度4 · 0 k P a下進行縮聚反應後，取得聚對苯二甲酸乙醇酯低聚 物。再將該低聚物連續供於最終縮聚反應器後，於溫度 295〜30CTC，真空度0 · 2kPa下進行縮聚反應 。所取得聚對苯二甲酸乙二醇酯聚合物之固有黏度（鄰氯 苯酚中3 5 °C下經測定之溶液粘度換算出値）爲〇 . 6 2 者，此藉由齒輪泵取出後，於造粒化步驟進行顆粒化。 又，將含有0 · 7重量％之初期縮聚反應器及最終縮 聚反應器之甲醇及1 · 5重量％之水的乙二醇飽出液以9 k g/h r之速度下，於昇溫器1 8昇溫至1 5 0°C後’ 介著配管1 0供入急驟蒸餾器1 1。另外’急驟蒸簡器 1 1之操作壓力調成27kPa。於急驟蒸觀器1 1分離 (請先閲讀背面之注意事項再填寫本頁) ▼裝· -訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 23 - 583216 A7 B7 五、發明説明（21) 低沸點物後之乙二醇成分含有0 · 0 ；[重量％之甲醇及 〇·04重量％之水。此乙二醇成份於9kg/hr下介 著配管8供於酯交換反應器1之後，做成部份啓始原料之 一醇’再利用之。又，此時，由配管6之乙二醇供給量爲 減至1 2kg/h r者。 〔實施例5〕 圖2中，將3 7 k g/hr之由配管5之對苯二甲酸 二甲酯與2 1 k g/h r之由配管6之乙二醇、以及 0 · 0 1 k g / h r之醋酸錳四水鹽連續供入酯交換反應 器後，於溫度200〜240 t，常壓下進行酯交換反應 ，餾出甲醇後，取得含有雙羥乙基對苯二甲酸酯之低分子 量聚合物。再將該含有雙羥乙基對苯二甲酸酯之低分子量 聚合物介著配管9後連續性供入初期縮聚反應器後，添加 〇· 02kg/hr三氧化銻後，於溫度290°C，真空 度4 . 0 k P a下進行縮聚反應之後，取得聚對苯二甲酸 乙二醇酯低聚合物。再將該低聚合物連續性供與最終縮聚 反應器後，於溫度295〜300t，真空度〇·2 k P a下進行縮聚反應。所取得聚對苯二甲酸乙二醇酯聚 合物之固有粘度（鄰氯苯酚中，3 5 °C下測定之溶液粘度 所算出之値）爲0 · 6 2者，此藉由齒輪泵取出後，於造 粒化步驟進行顆粒化。 又，將含有0 · 7重量％由初期縮聚反應及最終縮聚 反應器之甲醇及1 · 5重量分之水的乙二醇餾出液於9 (請先閱讀背面之注意事項再填寫本頁) 、11 線 經濟部智慧財產局g(工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 583216 經濟部智慧財產局員工消費合作社印製 A7 B7 _五、發明説明（22) k g / h r之速度下以昇溫器進行昇溫至1 5 0 °C後，介 著配管1 0供入酯交換反應器附屬蒸餾塔2。合倂由酯交 換反應器1往酯交換反應器附屬蒸餾塔2所餾出之4 k g / h r乙二醇成份後，合計1 3 k g / h i:於1 5 0 °C下 供入急驟蒸餾器1 1。又，急驟蒸餾器1 1之操作壓力調 整爲2 7 k P a。於急驟蒸餾器1 1分離低沸點物之乙二 醇成份含有〇·〇1重量％之甲醇及0·04重量％之水 。此乙二醇成份以1 3 k g / h r介著配管8供於酯交換 反應器1後做成部份啓發原料之二醇進行再利用。又，此 時由配管6之乙二醇供給量減爲1 2 k g / h r。 〔實施例6〕 圖3中，將3 7kg/h r之由配管5之對苯二甲酸 二甲酯與2 1 k g/h r之由配管6之乙二醇、以及 〇· 0 1 k g/h r醋酸錳四水鹽連續供入酯交換反應器 1後，於溫度200〜240 °C，常壓下，進行酯交換反 應，餾出甲醇後，取得含雙羥乙基對苯二甲酸酯之低分子 量聚合物，介著配管9後連續供入初期縮聚反應器後，添 加0 · 0 2 k g / h r之三氧化銻之後，於溫度2 9 0 °C ，真空度4 . 0 k P a下進行縮聚反應後，取得聚對苯二 甲酸乙二醇酯低聚合物。再將取得低聚物連續供入最終縮 聚反應於溫度295〜300 t，真空度0 · 2kPa下 進行縮聚反應。所取得聚對苯二甲酸乙二醇酯聚合物之固 有粘度（鄰氯苯酚中，3 5 °C下測定之溶液粘度所算出之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) ’裝· 、?! 線一 -25- 583216 A7 B7 五、發明説明（23 ) 値）爲0 · 6 2者，此藉由齒輪泵取出後，於造粒化步驟 進行顆粒化。 又，將〇.7重量％之由初期縮聚反應器及最終縮聚 反應器之甲醇及1 · 5重量％水所含之乙二醇餾出液以9 k g/h r之速度於昇溫器2 6昇溫至1 4 0°C後，介著 配管2 5供於急驟蒸餾器2 1。另外，急驟蒸餾器2 1之 操作壓力調成2 7 k P a。於急驟蒸餾器2 1分離低沸點 物之乙二醇成份爲含有0·03重量％甲醇、0·10重 量％之水。再使該乙二醇成份於昇溫器1 8昇溫至1 5 〇 t後，介著配管1 0供入酯交換反應器附屬蒸餾塔2。合 倂4 k g / h r之由酯交換反應器1往蒸餾塔2餾出之乙 二醇成份後，以合計1 3 k g / h r於1 5 0 °C下供入急 驟蒸餾器1 1。又，急驟蒸餾器1 1之操作壓力調爲 2 7 k P a者。於急驟蒸餾器1 1分離低沸點物後之乙二 醇成份含有〇·〇1重量％甲醇、及〇·〇5重量％水。 此乙二醇成份以1 3 k g / h r介著配管8供給於酯交換 反應器1後，做爲部份啓始原料之二醇再利用之。又，此 時由配管6之乙二醇供給量減至1 2 k g / h r者。 以上實施例1〜實施例6中所說明之聚對苯二甲酸乙 二醇酯的連續製造方法中，該含有由縮聚反應步驟所產生 之低沸點物二醇成份無需於系外個別大型之蒸餾裝置進行 精製，即使做爲部份原料再利用仍不致阻礙觸媒活性，可 安定生產之。 Γ請先閲讀背面之注意事項再填寫本頁，> -訂· 線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -26- 583216 A7 B7 五、發明説明（24) 〔實施例7〕 0¾ (請先閱讀背面之注意事項存填寫本X) 圖1中，將3 7kg/h r之由配管5之對苯二甲酸 二甲酯與由配管6之2 1 kg/h r乙二醇、以及 0 · 0 1 k g / h r之醋酸錳四水鹽連續供入酯交換反應 器1 ，於溫度200〜240 t，常壓下進行酯交換反應 ，餾出甲醇後，取得含雙羥乙基對苯二甲酸酯之低分子量 聚合物。再將該含雙羥乙基對苯二甲酸酯低分子量聚合物 介著配管9連續供入初期縮聚反應器後，添加0 · 0 2 kg/h r之三氧化銻，於溫度290 °C，真空度4 · 0 k P a下進行縮聚反應後，取得聚對苯二甲酸乙二醇酯低 聚物。再將該低聚合物連續供於最終縮聚反應器後，於溫 度295〜30CTC，真空度〇 · 2kPa下進行縮聚反 應。該聚對苯二甲酸乙二醇酯聚合物之固有粘度（鄰氯苯 酚中3 5 t測定之溶液粘度算出之値）爲〇 . 6 2者，此 藉由齒輪泵取出後，於造粒化步驟進行顆粒化。 經濟部智慧財產局員工消費合作社印製 又，將含有0 · 7重量％之初期縮聚反應器及最終縮 聚反應器之甲醇、1 ，4重量％水、及400重量PPm 之2 -甲基—1 ，3 —二氧雜環戊烷之乙二醇以9 kg/ h r供與後於昇溫器1 8進行昇溫至1 5 5 °C ’介著配管 1 0供於急驟蒸餾器1 1者。又，急驟蒸餾器1 1之操作 壓力調爲2 7 k P a。於急驟蒸餾器1 1分離低沸點物之 乙二醇成份爲含有0·01重量％甲醇、〇·〇3重量％ 水及40重量ppm 2 -甲基—1，3 —二氧雜環戊院 者。該乙二醇成份以9 k g / h r介著配管8供入酷交換 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583216 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（25 ) 反應器1後，做爲部份啓始原料之二醇進行再利用。又， 此時由配管6之乙二醇供給量減至1 2 k g / h r者。 此實施之聚對苯二甲酸乙二醇酯的連續製造方法中， 即使將含縮聚反應步驟產生之低沸點物二醇成份未於系外 個別以大型蒸餾裝置進行精製，做爲部份原料再利用後仍 不致阻礙觸媒活性，可安定生產之，且，製品聚對苯二甲 酸乙二醇酯之色調良好，L値爲6 · 8、b値爲+ 1 · 5 者。 〔實施例8〕 圖1中，將3 7kg/h r之由配管5之對苯二甲酸 二甲酯與2 1 k g/h r之由配管6之乙二醇，以及 0 · 0 1 k g / h r之醋酸錳四水鹽，連續供於酯交換反 應器1，於溫度200〜240 °C，常壓下進行酯交換反 應後，餾出甲醇，取得含有雙羥乙基對苯二甲酸酯之低分 子聚合物。再將該含雙羥乙基對苯二甲酸酯之低分子量聚 合物介著配管9連續供入初期縮聚反應器，添加0 · 0 2 kg/hr三氧化銻後，於溫度29CTC，真空度4 · 0 k P a下進行縮聚反應後，取得聚對苯二甲酸乙二醇酯低 聚合物。再將該低聚合物連續供與最終縮聚反應器後，於 溫度295〜30〇。(：，真空度〇 · 2kPa下進行縮聚 反應。該聚對苯二甲酸乙二醇酯聚合物之固有粘度（鄰氯 苯酚中3 5 °C下測定之溶液粘度算出之値）爲〇 · 6 2者 ，將此藉由齒輪泵取出後，於造粒化步驟進行顆粒化。 (請先閱讀背面之注意事項再填寫本頁} 、11 線· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羡） -28 - 583216 經濟部智慧財產局員工消費合作社印製 A7 B7 _五、發明説明（27 ) 且酯交換反應槽所附屬之蒸餾塔蒸餾負荷出現變動’無法 安定運轉。又，此所產生之製品聚對苯二甲酸乙二醇酯之 色調其L値爲60、 b値爲+3·0者。 以下，針對採用1，3 -丙二醇做爲碳數2〜4之亞 烷二醇時，進行說明。 〔實施例9〕 圖1中，將37kg/ hr由配管之對苯二甲酸二甲 酯與22kg/hr由配管6之1 ，3 —丙二醇及 〇· 0 3 k g / h r之鈦酸四丁氧金屬連續供入酯交換反 應器1，於溫度2 0 0〜2 2 0°C，常壓下進行酯交換反 應，餾出甲醇後取得含有雙羥丙基對苯二甲酸酯之低分子 量聚合物。再該該雙羥基丙基對苯二甲酸酯之低分子量聚 合物介著配管9連續供入初期縮聚反應器’於2 3 5 °C， 真空度4 · 0 k P a下進行縮聚反應，取得聚丙烯對苯二 甲酸酯低聚合物。再將該低聚合物連續供入縮聚反應器’ 於溫度247〜248°C，真空度〇 · 2kPa下進行縮 聚反應。所取得聚丙烯對苯二甲酸酯聚合物之固有粘度（ 鄰氯苯酚中3 5 °C測定之溶液粘度算出値）爲0 . 6 2 ’ 此藉由齒輪泵取出後，於造粒化步驟進行顆粒化。 又，將含有5 0 0重量p pm之初期縮聚反應器及最 終縮聚反應器之烯丙醇、2重量％甲醇及〇·7重量％水 之1，3 -丙二醇餾出液以7 · 5 k g / h r於昇溫器 1 8昇溫至2 0 0 °C後，介著配管1 〇供給於急驟蒸餾器 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) - 一 (請先閱讀背面之注意事項再填寫本頁) 583216 A7 ___ B7 _ 五、發明説明（28) 1 1。又，急驟蒸餾器1 1之操作壓力調整爲1 3 k P a 。於急驟蒸餾器1 1分離低沸點物後之1，3 -丙二醇成 份含有150重量ppm之烯丙醇、0·3重量％之甲醇 及0 · 2重量％水者。此1，3 -丙二醇成份以7kg/ h r介著配管8供入酯交換反應器1後，做成部份啓始原 料之二醇進行再利用。又，此時由配管6之1，3 —丙二 醇供給量減至1 5 k g / h r。 〔實施例1 0〕 圖2中，使3 7kg/h r由配管5之對苯二甲酸二 曱酯與2 2kg/hr由配管6之1，3 —丙二醇及 〇.0 3 k g/h r之鈦酸四丁氧金屬連續供入酯交換反 .應器1後，於溫度2 0 0〜2 2 0 °C，常壓下進行酯交換 反應，餾出甲醇後，取得含雙羥丙基對苯二甲酸酯之低子 量聚合物。再將該含雙羥丙基對苯二甲酸酯之低分子量聚 合物介著配管9連續供入初期縮聚反應器，於溫度2 3 5 °C，真空度4 · 0 k P a下進行縮聚反應，取得聚丙烯對 苯二甲酸酯。再將此低聚合物連續供入最終縮聚反應器’ 於溫度247〜248°C ’真空度0 · 2kPa下進行縮 聚反應。所取得聚丙烯對苯二甲酸酯聚合物之固有粘度（ 鄰氯苯酚中3 5 °C測定之溶液粘度算出値）爲〇 · 6 ’此 藉由齒輪泵取出後’於造粒化步驟進行顆粒化。 又，將含有500重量PPm烯丙醇、2重量％甲醇 及〇· 7重量％水之1 ’ 3 —丙二醇I留出液以7 · 5 kg 本紙張尺度適用中國國家標隼（CNS ) A4規格（2K)X297公釐） -31 - * _ ---------•裝-- (請先閱讀背面之注意事項再填寫本頁) 、1Τ 線_ 經濟部智慧財產局Μ工消費合作社印製 583216 A 7 __________ B7 _ 五、發明説明（29 ) / h r於昇溫器1 8昇溫至2 0 0 °C後，介著配管1 〇供 入酯交換反應器附屬蒸餾塔2。合倂4 k g / h r之由酯 交換反應器1往酯交換反應器附屬蒸餾塔2所餾出之1 ’ 3 —丙二醇成份後，以合計11 · 5kg/hr ，200 °C下供急驟蒸餾器1 1。又，急驟蒸餾器1 1之操作壓力 調成1 3 k P a。於急驟蒸餾器1 1分離低沸點物後之1 ，3 —丙二醇成份含有1〇重量ppm之烯丙醇、0 · 1 重量％以下之甲醇及〇 . 1重量％以下之水。將此1，3 一丙二醇成份以9 k g/h r介著配管8供入酯交換反應 器1後，做爲部份啓始原料，再利用之。又，此時，由配 管6之1，3 -丙二醇供給量減至17kg/hi:。 〔實施例1 1〕 圖3中，使3 7 k g/h r由配管5之對苯二甲酸二 甲酯與22kg/hr由配管6之1 ，3 —丙二醇及 〇· 〇 3 k g/h r之鈦酸四丁氧金屬連續供入酯交換反 應器1 ，於溫度2 0 0〜2 2 0 °C，常壓下進行酯交換反 應，餾出甲醇後，取得含有雙羥丙基對苯二甲酸酯之低分 子量聚合體。再將該含雙羥丙基對苯二甲酸之低分子量聚 合物介著配管9連續供入初期縮聚反應器，於溫度2 3 5 t，真空度4 · 0 k P a下進行縮聚反應後，取得聚丙烯 對苯二甲酸酯低聚合物。再將該低聚合物連續供入最終縮 聚反應器，於溫度247〜248 °C，真空度〇 · 2 k P a下進行縮聚反應。所取得聚丙烯對苯二甲酸酯聚合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) 一" ' - (請先閱讀背面之注意事項再填寫本頁)、 1T line 583216 A7 _ B7 Production cooperation of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed 5. Description of the invention (19) The 1,4-butanediol distillate of water was heated at 7 kg / hr in a heater 2 6 After the temperature reached 150 ° C, the flash still 21 was supplied through a pipe 25. The operating pressure of the flash still 21 was adjusted to 27 kPa. After the low-boiling point was separated in the flash still 21, 1,4-butanediol contained 0.2% by weight of tetrahydrofuran, 2% by weight of methanol, and 0.3% by weight of water. This 1,4-butanediol component was further heated to 150 ° C in a temperature riser, and then fed to the transesterification reactor 2 attached to the transesterification reactor through a pipe 10. The combined 1,4-butanediol component distilled from the transesterification reactor 1 to the distillation column 2 was 4 k g / h r, and a total of 11 k g / h r was fed to the flash still 11 at 150 t. Also, the operating pressure of the flash still 11 was adjusted to 27 kPa. After the low-boiling point was separated by 11 points in the flash still, the 1,4-butanediol component contained tetrahydrofuran of 0. 1% by weight or less, methanol of 0.1% by weight or less, and water of 0.1% by weight. This 1,4-butanediol component was fed to the transesterification reactor 1 at 10 kg / hr through a pipe 8 to prepare a diol partially inspired by the raw material and reused. At this time, the 1,4-butanediol supply amount from the pipe 6 was reduced to 18 kg / hr. In the continuous manufacturing method of polybutylene terephthalate described in the above embodiment, the low-boiling point diol component produced by the polycondensation reaction step does not need to be separately refined outside the system by using a large distillation device as a part Even if the raw material is reused, it will not hinder the catalyst activity, and it can be produced stably. In the following, the case where an alkylene glycol having 2 to 4 carbon atoms is used as the ethyl alcohol is described. In addition, the hue in the examples were measured by a welding-type color machine (Σ 8 0 manufactured by Nippon Denshoku Industries Co., Ltd.), and L and b 値 were determined after measurement. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 77 ^ (Please read the precautions on the back before filling in this page) _packing · 、 11 wire 5832l6 Α7 、 ^ ----- Β7 __ 5 2. Description of the invention (20) L 値 stands for bright, and higher L 値 stands for bright hue polymer. b 値 represents yellow to cyan, and the lower b 値, the hue polymer with less yellowing. [Example 4] In Fig. 1, 37 kg / hr is transferred from pipe 5 dimethyl terephthalate, After 21 kg / hr of ethylene glycol from piping 6 and manganese acetate tetrahydrate of 0.01 kg / hr were continuously fed into the transesterification reactor 1, the ester was carried out at a temperature of 2000 to 2400 t under normal pressure. The exchange reaction was followed by distillation of methanol to obtain a low molecular weight polymer containing bishydroxyethyl terephthalate. The low-molecular-weight polymer containing dihydroxyethyl terephthalate was continuously fed into the initial polycondensation reactor through a pipe 9, and after adding antimony trioxide of 0. 0 2 kg / hr, the temperature was 2 9 0 After carrying out the polycondensation reaction at ° C and a vacuum of 4.0 kPa, a polyethylene terephthalate oligomer was obtained. The oligomer was continuously supplied to the final polycondensation reactor, and then the polycondensation reaction was performed at a temperature of 295 to 30 CTC and a vacuum degree of 0 · 2 kPa. The inherent viscosity of the obtained polyethylene terephthalate polymer (converted by measuring the viscosity of the solution measured at 35 ° C in o-chlorophenol) is 0.62, which is taken out by a gear pump, Granulation is performed in a granulation step. In addition, an ethylene glycol saturated solution containing methanol in the initial polycondensation reactor and final polycondensation reactor of 0.7% by weight and 1.5% by weight of water in a final polycondensation reactor was heated at a temperature of 9 kg / hr at a temperature of 1 8 After the temperature rises to 150 ° C, it is supplied to the flash still 11 through a pipe 10. In addition, the operating pressure of the 'steamer 11' was adjusted to 27 kPa. Separate from the rapid steaming viewer 1 (Please read the precautions on the back before filling this page) ▼ Packing--Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives Paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 (Mm) _ 23-583216 A7 B7 V. Description of the invention (21) The ethylene glycol component after low boiling point contains 0 · 0; [wt% methanol and 0.04 wt% water. This ethylene glycol component was supplied to the transesterification reactor 1 through a piping 8 at 9 kg / hr, and then was used as a part of the starting material of a mono-alcohol '. At this time, the amount of ethylene glycol supplied from the pipe 6 was reduced to 12 kg / hr. [Example 5] In FIG. 2, 37 kg / hr of dimethyl terephthalate from the pipe 5 and 21 kg / hr of ethylene glycol from the pipe 6 and 0. 0 1 kg / hr After the manganese acetate tetrahydrate was continuously fed into the transesterification reactor, the transesterification reaction was performed at a temperature of 200 to 240 t under normal pressure. After the methanol was distilled off, a low molecular weight containing dihydroxyethyl terephthalate was obtained. polymer. The low-molecular-weight polymer containing dihydroxyethyl terephthalate was continuously fed into the initial polycondensation reactor through the pipe 9, and after adding 0.02 kg / hr of antimony trioxide, the temperature was 290 ° C. After carrying out the polycondensation reaction at a vacuum degree of 4.0 k Pa, a polyethylene terephthalate oligomer was obtained. After the low polymer continuity was supplied to the final polycondensation reactor, the polycondensation reaction was performed at a temperature of 295 to 300 t and a degree of vacuum of 0.2 kPa. The intrinsic viscosity of the obtained polyethylene terephthalate polymer (calculated from the viscosity of the solution measured at 35 ° C in o-chlorophenol) was 0 · 62, and this was taken out by a gear pump In the granulation step, granulation is performed. In addition, the ethylene distillate containing 0. 7 wt% of methanol and 1.5 parts by weight of water from the initial polycondensation reaction and the final polycondensation reactor was 9 (please read the precautions on the back before filling this page) , 11 Intellectual Property Bureau of the Ministry of Economic Affairs g (printed by the Industrial and Consumer Cooperatives, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -24- 583216, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, A7 B7 _Five 、 Explanation of the invention (22) After the temperature is raised to 150 ° C with a temperature riser at a rate of kg / hr, it is supplied to the distillation column 2 attached to the transesterification reactor through the pipe 10. The mixture is transferred from the transesterification reactor 1 to After the 4 kg / hr ethylene glycol component distilled from the distillation column 2 attached to the transesterification reactor, a total of 13 kg / hi was supplied to the flash still 11 at 150 ° C. The flash still 1 The operating pressure of 1 was adjusted to 27 kPa. The ethylene glycol component separated from the low-boiling point in the flash still 1 contained 0.001% by weight of methanol and 0.04% by weight of water. This ethylene glycol component It was made into 1 part of the heuristic raw material after supplying it to the transesterification reactor 1 at 1 3 kg / hr through the pipe 8. Reuse. At this time, the amount of ethylene glycol supplied from the pipe 6 is reduced to 12 kg / hr. [Example 6] In FIG. 3, 37 kg / hr of dimethyl terephthalate from the pipe 5 is used. Ester and 2 1 kg / hr of ethylene glycol from piping 6 and 0.001 kg / hr of manganese acetate tetrahydrate were continuously fed into the transesterification reactor 1 at a temperature of 200 to 240 ° C under normal pressure. After carrying out the transesterification reaction, after distilling off methanol, a low-molecular-weight polymer containing dihydroxyethyl terephthalate was obtained. After being continuously fed into the initial polycondensation reactor through the pipe 9, 0. 0 2 kg / After hr of antimony trioxide, a polycondensation reaction was performed at a temperature of 290 ° C and a vacuum of 4.0 kPa to obtain a polyethylene terephthalate oligomer. The oligomer was continuously obtained The final polycondensation reaction is carried out at a temperature of 295 ~ 300 t and a vacuum of 0 · 2kPa. The inherent viscosity of the obtained polyethylene terephthalate polymer (in o-chlorophenol, measured at 3 5 ° C) The paper size calculated from the solution viscosity is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the back first Please fill in this page again if you need to pay attention to the above.) 'Installation ·,?! Line 1-25- 583216 A7 B7 V. Description of the invention (23) 値) is 0 · 62, which is taken out by a gear pump and then granulated. The granulation step was granulated. In addition, 0.7% by weight of the distillate of ethylene glycol contained in methanol and 1.5% by weight of water from the initial polycondensation reactor and the final polycondensation reactor was at a rate of 9 kg / hr. After the temperature of the temperature increaser 26 was increased to 140 ° C, the temperature was increased to 140 ° C, and then supplied to the flash still 21 through the pipe 25. In addition, the operating pressure of the flash still 21 was adjusted to 27 kPa. The ethylene glycol component of the low boiling point separated in the flash still 21 was water containing 0.03% by weight of methanol and 0.10% by weight. The ethylene glycol component was further heated to 15Ot in a temperature increaser 18, and then fed to a distillation column 2 attached to the transesterification reactor through a pipe 10. After a total of 4 k g / h r of ethylene glycol components distilled from the transesterification reactor 1 to the distillation column 2, a total of 13 k g / h r was supplied to the flash still 11 at 150 ° C. The operating pressure of the flash still 11 was adjusted to 27 kPa. The ethylene glycol component after the low-boiling point was separated in the flash still 11 contained 0.001% by weight of methanol and 0.05% by weight of water. This ethylene glycol component was supplied to the transesterification reactor 1 at a rate of 13 kg / hr through a pipe 8 and reused as a part of the diol as the starting material. At this time, the supply amount of ethylene glycol from the pipe 6 was reduced to 12 k g / h r. In the continuous manufacturing method of polyethylene terephthalate described in the above Examples 1 to 6, the diol component containing the low-boiling point diol produced by the polycondensation reaction step does not need to be separately distilled outside the system. The device is refined, and even if it is reused as part of the raw material, it does not hinder the catalyst activity, and it can be produced stably. Γ Please read the notes on the back before filling in this page, >-Order · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Online Economics This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -26- 583216 A7 B7 V. Explanation of the invention (24) [Example 7] 0¾ (Please read the precautions on the back and fill in this X) In Figure 1, 3.7 kg / hr of dimethyl terephthalate from pipe 5 and 2 1 kg / hr of ethylene glycol from pipe 6 and manganese acetate tetrahydrate of 0. 01 kg / hr were continuously fed into the transesterification reactor 1 at a temperature of 200 to 240 t under normal pressure. After distilling off methanol, a low molecular weight polymer containing bishydroxyethyl terephthalate was obtained. The dihydroxyethyl terephthalate-containing low-molecular-weight polymer was continuously fed into the initial polycondensation reactor through the pipe 9, and then antimony trioxide of 0. 0 2 kg / hr was added, and the temperature was 290 ° C. After performing a polycondensation reaction at a vacuum degree of 4.0 kPa, a polyethylene terephthalate oligomer was obtained. After the oligomer was continuously supplied to the final polycondensation reactor, the polycondensation reaction was performed at a temperature of 295 to 30 CTC and a vacuum of 0.2 kPa. The intrinsic viscosity of the polyethylene terephthalate polymer (calculated from the viscosity of the solution measured at 35 t in o-chlorophenol) was 0.62, which was taken out by a gear pump and then granulated. The steps are granulated. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the initial polycondensation reactor and final polycondensation reactor will contain 0.7% by weight of methanol, 1, 4% by weight of water, and 400% by weight of 2-methyl-1 PPm. The ethylene glycol of 3-dioxolane was supplied at 9 kg / hr, and then the temperature was raised to 1 5 5 ° C in a temperature increaser 18, and 1 was supplied to the flash still 11 through a pipe 10. The operating pressure of the flash still 11 was adjusted to 27 kPa. The ethylene glycol component separated from the low-boiling point in the flash distillation unit 11 contains 0.01% by weight of methanol, 0.03% by weight of water, and 40% by weight of 2-methyl-1,3-dioxolane. By. The ethylene glycol content is supplied at 9 kg / hr via piping 8 for cool exchange. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 583216 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (25) After the reactor 1, the diol is reused as a part of the starting material. At this time, the amount of ethylene glycol supplied from the pipe 6 is reduced to 12 k g / h r. In this method of continuous production of polyethylene terephthalate, even if the low-boiling point diol component containing the polycondensation reaction step is not separately refined outside the system by a large-scale distillation device, it is used as part of the raw material. After use, it does not hinder the catalyst activity, and it can be produced stably, and the color tone of the product polyethylene terephthalate is good, L 値 is 6 · 8, and b 値 is + 1 · 5. [Example 8] In FIG. 1, 37 kg / hr of dimethyl terephthalate from the pipe 5 and 21 kg / hr of ethylene glycol from the pipe 6 and 0. 0 1 kg / hr Manganese acetate tetrahydrate was continuously supplied to the transesterification reactor 1. After the transesterification reaction was performed at a temperature of 200 to 240 ° C under normal pressure, methanol was distilled off to obtain a low content of bishydroxyethyl terephthalate. Molecular polymer. The low-molecular-weight polymer containing dihydroxyethyl terephthalate was continuously fed into the initial polycondensation reactor through a pipe 9. After adding 0. 0 2 kg / hr of antimony trioxide, the temperature was 29CTC and the degree of vacuum After the polycondensation reaction was performed at 4.0 kPa, a polyethylene terephthalate oligomer was obtained. The oligomer was continuously fed to the final polycondensation reactor, and then the temperature was from 295 to 300. (: The polycondensation reaction is performed at a vacuum of 0.2 kPa. The intrinsic viscosity of the polyethylene terephthalate polymer (calculated by the viscosity of the solution measured at 35 ° C in o-chlorophenol) is 0.6 For two, take out this by a gear pump and then granulate it in the granulation step. (Please read the precautions on the back before filling out this page} 、 11-line · This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public envy) -28-583216 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _V. Description of the invention (27) And the distillation load attached to the distillation tower attached to the transesterification reaction tank has changed 'cannot run stably. Also, The resulting product has a color tone of polyethylene terephthalate whose L 値 is 60 and b 値 is + 3 · 0. In the following, 1,3-propanediol is used as the alkylene having 2 to 4 carbon atoms. [Example 9] In Fig. 1, 37 kg / hr of pipe dimethyl terephthalate and 22 kg / hr of pipe 6 of 1, 3-propanediol and 0.03 kg / hr hr of tetrabutyl metal titanate was continuously fed into the transesterification reactor 1 at a temperature of 2 0 0 At 220 ° C, a transesterification reaction was carried out at normal pressure. After distilling off methanol, a low molecular weight polymer containing bishydroxypropyl terephthalate was obtained. The low-molecular weight polymer was continuously fed into the initial polycondensation reactor through a pipe 9 to perform a polycondensation reaction at a temperature of 2 3 5 ° C and a vacuum of 4.0 kPa to obtain a polypropylene terephthalate low polymer. The low polymer was continuously fed into a polycondensation reactor 'to perform a polycondensation reaction at a temperature of 247 to 248 ° C and a vacuum of 0.2 kPa. The inherent viscosity of the obtained polypropylene terephthalate polymer (in o-chlorophenol) Calculate the viscosity of the solution measured at 35 ° C. 値) is 0.62 '. This is taken out by a gear pump, and then granulated in the granulation step. In addition, an initial polycondensation reactor containing 5000 weight p pm and After the 1,3-propanediol distillate of allyl alcohol, 2% by weight of methanol and 0.7% by weight of water in the final polycondensation reactor was heated at a temperature of 18 ° C to 200 ° C at a temperature of 7.5 kg / hr, It is supplied to the flash still through the pipe 10. The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm)-1 (Please read the precautions on the back before filling out this page) 583216 A7 ___ B7 _ 5. Description of the invention (28) 1 1. Also, the operating pressure of the flash still 1 1 is adjusted to 1 3 k P a. The 1,3-propanediol component after separating the low-boiling point in the flash distiller 11 contains 150% by weight of allyl alcohol, 0.3% by weight of methanol, and 0.2% by weight of water. This 1,3- After the propylene glycol component was fed into the transesterification reactor 1 through a pipe 8 at 7 kg / hr, a part of the diol was used as a starting material for reuse. At this time, the supply amount of 1,3-propanediol from the pipe 6 was reduced to 15 k g / h r. [Example 1 0] In Fig. 2, 37 kg / hr of dibutyl terephthalate from pipe 5 and 22 kg / hr of 1,3-propanediol of pipe 6 and 0.03 kg / hr of titanium were used. Tetraoxybutyric acid was continuously fed into the transesterification reactor. After the reactor 1, the transesterification reaction was performed at a temperature of 2000 to 220 ° C under normal pressure. After the methanol was distilled off, dihydroxypropyl-containing p-benzene was obtained. Low molecular weight polymer of diformate. The low-molecular-weight polymer containing bishydroxypropyl terephthalate was continuously fed into the initial polycondensation reactor through a pipe 9, and the polycondensation was performed at a temperature of 2 3 5 ° C and a vacuum degree of 4.0 kPa. Reaction to obtain polypropylene terephthalate. This oligomer was continuously fed into a final polycondensation reactor 'to perform a polycondensation reaction at a temperature of 247 to 248 ° C' and a vacuum degree of 0 · 2 kPa. The inherent viscosity of the obtained polypropylene terephthalate polymer (calculated from the solution viscosity measured at 35 ° C in o-chlorophenol) was 0.6. "This was taken out by a gear pump" in the granulation step Granulated. In addition, a 1 '3-propanediol I retentate solution containing 500% of PPm allyl alcohol, 2% by weight of methanol, and 0.7% by weight of water was used at a size of 7.5 kg. This paper is compliant with China National Standard (CNS) A4 (2K) X297 mm) -31-* _ --------- • equipment-(Please read the precautions on the back before filling out this page), 1T line_ Intellectual Property Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 583216 A 7 __________ B7 _ 5. Explanation of the invention (29) / hr After the temperature of the temperature riser 18 is increased to 200 ° C, it is supplied to the distillation tower 2 attached to the transesterification reactor through the pipe 10. After mixing 4 kg / hr from the transesterification reactor 1 to the distillation tower 2 attached to the transesterification reactor, the 1'3-propanediol component was distilled and supplied to the flash still at a total of 11.5 kg / hr at 200 ° C. 1 1. The operating pressure of the flash still 11 was adjusted to 13 kPa. After the low-boiling point was separated in the flash still 11, the 1,3-propanediol component contained 10% by weight of allyl alcohol, 0.1% by weight or less of methanol, and 0.1% by weight or less of water. This 1,3-propanediol component was fed to the transesterification reactor 1 at 9 kg / h r through a pipe 8 as a part of the starting material and reused. At this time, the supply of 1,3-propanediol from pipe 6 was reduced to 17 kg / hi :. [Example 1 1] In Fig. 3, 37 kg / hr of dimethyl terephthalate from piping 5 and 22 kg / hr of piping 6 from 1,3-propanediol and 0.3 kg / hr of titanium The acid tetrabutoxy metal is continuously fed into the transesterification reactor 1 and the transesterification reaction is performed at a temperature of 200 to 220 ° C under normal pressure. After distilling off the methanol, the dihydroxypropyl terephthalic acid is obtained. Low molecular weight polymer of ester. The low-molecular-weight polymer containing dihydroxypropyl terephthalic acid was continuously fed into the initial polycondensation reactor through a pipe 9 and subjected to a polycondensation reaction at a temperature of 2 3 5 t and a vacuum degree of 4.0 kPa. Obtained polypropylene terephthalate oligomer. The oligomer was continuously fed into the final polycondensation reactor, and the polycondensation reaction was performed at a temperature of 247 to 248 ° C and a degree of vacuum of 0.2 kPa. The obtained polypropylene terephthalate is polymerized. The size of this paper applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). I " '-(Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 583216 A7 B7 五、發明説明（30) 物之固有粘度.（鄰氯苯酚中，3 5 °C測定溶液粘度所算出 値）爲0 · 6 2，此藉由齒輪泵取出後’於造粒化步驟進 行顆粒化。 又，將含有5 0 0重量P pm由初期縮聚反應器及最 終縮聚反應器之烯丙醇、2重量％甲醇、及7重量％之水 的1，3 -丙二醇餾出液以7 · 5 k g / h r ’於昇溫器 2 6昇溫至2 0 0 °C後，介著配管2 5供入急驟蒸顧器 2 1。又，急驟蒸餾器2 1之操作壓力調爲1 3 k P a。 於急驟蒸餾器2 1分離低沸點物之1 ’ 3 -丙二醇成份含 有150重量Ppm之烯丙醇、0·3重量％甲醇及 〇· 2重量％水者。再將此1，3 -丙二醇成份於昇溫器 1 8再昇溫爲2 0 0°C後’介著配管1 0供入酯交換反應 器附屬蒸餾塔2。合倂4 k g / h r由酯交換反應器1往 蒸餾塔2餾出之1，3 -丙二醇成份後，以合計1 1 · 5 k g / h r於2 0 0 °C下供與急驟蒸餾器1 1。又，急驟 蒸餾器1 1之操作壓力調爲1 3 k P a。於急驟蒸餾器 1 1分離低沸點物後之1 ’ 3 -丙二醇成份含有1 0重量 ppm之烯丙醇、0·1重量％以下之甲醇、0·1重量 %以下之水。此1，3 —丙二醇成份以9kg/hr ，介 著配管8供入酯交換反應器1後，做爲部份啓發原料進行 再利用。又，此時，由配管6之1，3 —丙二醇供給量減 爲 17kg/hr。 以上實施例中所說明之聚丙烯對苯二甲酸酯的連續製 造方法中，含由縮聚反應步驟所產生低沸點物之二醇成份 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I--------•裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 583216 A7 B7五、發明説明（31 ) 未於系外個別大型蒸餾裝置進行精製，即使做爲部份原料 後再利用仍不致阻礙觸媒活性，可安定生產。 本發明係提供由芳香族二竣酸或其低級院酯與碳數2 〜4亞烷二醇做爲主要成份之二醇成份之聚酯連續進行製 造時，無需於系外精密裝置進行縮聚步驟所回收二醇成份 之精製，可藉小型急驟蒸餾設備之設置，且做成小含率少 ，純度高之原料再利用之，可達成削減運轉經費與設備簡 化之效果，更可連續製造安定、價廉之聚酯之極明顯有效 之方法者。 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局Μ工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -34-, 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 583216 A7 B7 V. Description of the invention (30) The intrinsic viscosity of the substance (in o-chlorophenol, calculated by measuring the viscosity of the solution at 3 5 ° CC) is 0 · 6 2 ， After this is taken out by a gear pump, granulation is performed in a granulation step. In addition, a 1,3-propanediol distillate containing 5000 weight P pm of allyl alcohol, 2% by weight of methanol, and 7% by weight of water from the initial polycondensation reactor and the final polycondensation reactor was adjusted to 7.5 kg. / hr 'After the temperature of the temperature riser 26 is increased to 200 ° C, the steam steamer 21 is supplied through the pipe 25. The operating pressure of the flash still 21 was adjusted to 1 kPa. The 1 ' 3-propanediol component of the low-boiling point was separated in a flash still 21 containing 150% by weight of allyl alcohol, 0.3% by weight of methanol, and 0.2% by weight of water. Then, the 1,3-propanediol component was further heated to 200 ° C in a temperature riser 18 and then fed to a distillation column 2 attached to the transesterification reactor through a pipe 10. Combined 4 kg / hr from the transesterification reactor 1 to the distillation column 2 of the 1,3-propanediol component, and then supplied to the flash still at a total of 1 1 · 5 kg / hr at 20 ° C 1 1 . The operating pressure of the flash still 11 was adjusted to 1 kPa. The 1'3-propanediol component after separating the low-boiling point in the flash still 11 contains 10% by weight of allyl alcohol, 0.1% by weight or less of methanol, and 0.1% by weight or less of water. The 1,3-propanediol component was fed to the transesterification reactor 1 at a rate of 9 kg / hr through a pipe 8 and reused as part of the heuristic material. At this time, the supply of 1,3-propanediol from the pipe 6 was reduced to 17 kg / hr. In the continuous manufacturing method of polypropylene terephthalate described in the above embodiments, the diol component containing low-boiling substances produced by the polycondensation reaction step is applicable to the Chinese National Standard (CNS) A4 specification (210X297). Li) I -------- • Installation-- (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives 583216 A7 B7 V. Description of the invention (31) Refined in some large-scale distillation units outside the system, even if used as part of the raw material, it does not hinder the catalyst activity, and can be produced stably. The present invention provides the continuous production of a polyester comprising an aromatic dibasic acid or a lower grade ester thereof and a diol component having a carbon number of 2 to 4 as the main component without the need for a polycondensation step in an external precision device. Refined diol components can be refined by setting up small-scale flash distillation equipment, and made into small-scale, low-purity, high-purity raw materials for reuse, which can achieve the effect of reducing operating expenses and simplifying equipment. Extremely effective method for cheap polyester. (Please read the precautions on the back before filling out this page) Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -34-

Claims (1)

58325832 A8 B8 C8 D8 六、申請專利範圍 1 . 一種芳香族聚酯之連續製造方法’其特徵係1種 選自以芳香族二羧酸爲主要二羧酸成份’乙二醇、1 ’ 3 一丙二醇、及1，4 一丁 —*醇所成群之一^醇做爲一*醇成份 之芳香族聚酯經由酯化或酯交換反應及縮聚反應後’進行 連續製造之方法者，含有由該縮聚反應之該二醇餾出液至 少附於急驟蒸餾後去除低沸點之後’使至少部份殘留液於 該酯化或酯交換反應做爲部份該二醇進行循環使用之。 2 .如申請專利範圍第1項之方法，其中該方法係使 含由縮聚反應之該二醇餾出液於附於該急驟蒸餾之前’供 入酯交換或酯化反應實施步驟所附屬之蒸餾塔後’其蒸餾 塔之殘留排出液附於該急驟蒸餾者。 3 .如申請專利範圍第1項之方法，其中該方法係使 含由縮聚反應之該二醇餾出液於附於第1急驟蒸餾與第2 急驟蒸餾所成之急驟蒸餾後，於將第1急驟蒸餾之殘留液 附於第2急驟蒸餾之前供入酯交換或酯化反應之實施步驟 所附屬蒸餾塔後，再將此蒸餾塔之殘留排出液附於該第2 急驟蒸餾。 4 .如申請專利範圍第1項至第3項中任一項之方法 ，其中該方法係將以1，4 - 丁二醇做爲主要二醇成份之 芳香族聚酯於酯交換或酯化反應中其使做爲該殘留液者之 水份含率爲0 · 5重量％以下之殘留液進行循環使用後， 進行製造者。 5 ·如申請專利範圍第1項至第3項中任一項之方法 ，其中經由酯交換反應及縮聚反應後，以乙二醇做爲主要 本紙張尺度適用中國國家梂參（CNS ) A4規格（210X297公釐） _ 35 _ — --------— (請先閲讀背面之注意事項再填寫本頁) 訂 線 經濟部智慧財產局員工消費合作社印製 583216 A8 B8 C8 D8 六、申請專利範圍 二醇成份之芳香族聚酯於酯交換反應中，做爲該殘留液之 水份含率爲0 · 〇 5重量％以下之殘留液進行循環使用後 ，進行製造之。 6 ·如申請專利範圍第1項至第3項中任一項之方法 ’其中該方法係以乙二醇做爲主要二醇成份之芳香族聚酯 於酯交換或酯化反應中做爲.該殘留液之2 -甲基- 1，3 -二氧雜環戊烷之含有率爲5 〇 p p m以之殘留液進行循 環使用後進行製造之。 7 ·如申請專利範圍第1項至第3項中任一項之方法 ’其中該方法係使以乙二醇做爲主要二醇成份之芳香族聚 酯於酯交換或酯化反應中，做爲該殘留液之甲基溶纖劑含 率爲1 0 P P m以下之殘留液進行循環使用後，製造之。 8 ·如申請專利範圍第1項至第3項中任一項之方法 ，其中該方法係使以1，3 -丙二醇爲主要二醇成份之芳 香族聚酯於酯交換或酯化反應中，做爲該殘留液之水份含 率爲0 · 5重量％以下之殘留液進行循環使用後，製造之 t I ---------- (請先閱讀背面之注意事項再填寫本頁) 、1T 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 36 _A8 B8 C8 D8 6. Scope of Patent Application 1. A continuous production method of aromatic polyesters, which is characterized by a type selected from the group consisting of aromatic dicarboxylic acids as the main dicarboxylic acid components, ethylene glycol, 1 and 3 monopropylene glycol. And 1,4 Butyl- * alcohol is one of the group of ^ alcohol as a * alcohol component of the aromatic polyester through the esterification or transesterification reaction and polycondensation reaction 'continuous manufacturing method, including by the The diol distillate of the polycondensation reaction is attached at least after the rapid distillation to remove the low boiling point, so that at least part of the residual liquid is recycled in the esterification or transesterification reaction as part of the diol. 2. The method according to item 1 of the scope of patent application, wherein the method is such that the diol distillate containing the polycondensation reaction is supplied to the distillation attached to the transesterification or esterification reaction implementation step before being attached to the flash distillation. Behind the column, the residual effluent from its distillation column is attached to the flash distillation. 3. The method according to item 1 of the scope of patent application, wherein the method is such that the diol distillate containing the polycondensation reaction is attached to the first and second flash distillations, and the first 1 The residual liquid of the flash distillation is attached to the second flash distillation before being supplied to the distillation column attached to the transesterification or esterification reaction step before the second flash distillation. 4. The method according to any one of claims 1 to 3 in the scope of patent application, wherein the method is to transesterify or esterify an aromatic polyester with 1,4-butanediol as the main diol component In the reaction, the residual liquid having a water content of 0.5% by weight or less as the residual liquid is recycled and used by the manufacturer. 5 · The method according to any one of claims 1 to 3, wherein after transesterification reaction and polycondensation reaction, ethylene glycol is used as the main paper standard. The Chinese National Ginseng (CNS) A4 specification is applicable. (210X297 mm) _ 35 _ — --------— (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 583216 A8 B8 C8 D8 The aromatic polyester with a diol component in the scope of the patent application is used in the transesterification reaction as a residual liquid with a moisture content of 0. 05 wt% or less to be recycled and then manufactured. 6.The method according to any one of the items 1 to 3 of the scope of the patent application, wherein the method is an aromatic polyester using ethylene glycol as the main diol component in the transesterification or esterification reaction. The residual liquid having a 2-methyl-1,3-dioxolane content of 50 ppm was produced by recycling the residual liquid. 7 · The method according to any one of items 1 to 3 of the scope of the patent application, wherein the method is to use an aromatic polyester with ethylene glycol as the main diol component in the transesterification or esterification reaction, and do The residual liquid having a methylcellosolve content of 10 PP m or less was recycled and then manufactured. 8. The method according to any one of claims 1 to 3 in the scope of patent application, wherein the method is to use an aromatic polyester with 1,3-propanediol as the main diol component in a transesterification or esterification reaction, As the residual liquid with a moisture content of 0. 5 wt.% Or less, the residual liquid is recycled after t i ---------- (Please read the precautions on the back before filling in this Page), 1T Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210X297 mm) _ 36 _
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Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6906164B2 (en) * 2000-12-07 2005-06-14 Eastman Chemical Company Polyester process using a pipe reactor
CN1297585C (en) * 2002-09-20 2007-01-31 三菱化学株式会社 Process of producing polyesters
ES2416337T3 (en) 2005-11-22 2013-07-31 Segetis, Inc. Ketals of glycerol levulinate and its use
US7524921B2 (en) 2005-12-21 2009-04-28 E. I. Du Pont De Nemours And Company Continuous manufacture of poly(trimethylene terephthalate)
US7531617B2 (en) * 2005-12-21 2009-05-12 E. I. Du Pont De Nemours And Company Continuous process for producing poly(trimethylene terephthalate)
US7504474B2 (en) * 2005-12-21 2009-03-17 E. I. Du Pont De Nemours And Company Poly(trimethylene therephthalate) continuous manufacturing process
US7906598B2 (en) * 2006-08-30 2011-03-15 Intertape Polymer Corp. Recirculation loop reactor bulk polymerization process
US20100105847A1 (en) 2006-01-24 2010-04-29 Intertape Polymer Corp. Plug flow bulk polymerization of vinyl monomers
JP4848806B2 (en) * 2006-03-24 2011-12-28 東洋紡績株式会社 Method for producing copolyester
JP5034335B2 (en) * 2006-06-19 2012-09-26 東洋紡績株式会社 Continuous production method of copolyester
JP2010502786A (en) * 2006-08-30 2010-01-28 インターテープ ポリマー コーポレーション Bulk polymerization process with recirculation loop reactor
JP5076437B2 (en) * 2006-10-11 2012-11-21 東洋紡績株式会社 Polyester manufacturing method
US7649109B2 (en) * 2006-12-07 2010-01-19 Eastman Chemical Company Polyester production system employing recirculation of hot alcohol to esterification zone
US7943094B2 (en) 2006-12-07 2011-05-17 Grupo Petrotemex, S.A. De C.V. Polyester production system employing horizontally elongated esterification vessel
US7892498B2 (en) * 2007-03-08 2011-02-22 Eastman Chemical Company Polyester production system employing an unagitated esterification reactor
US7863477B2 (en) 2007-03-08 2011-01-04 Eastman Chemical Company Polyester production system employing hot paste to esterification zone
US7847053B2 (en) 2007-07-12 2010-12-07 Eastman Chemical Company Multi-level tubular reactor with oppositely extending segments
US7872090B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Reactor system with optimized heating and phase separation
US7872089B2 (en) 2007-07-12 2011-01-18 Eastman Chemical Company Multi-level tubular reactor with internal tray
US7858730B2 (en) 2007-07-12 2010-12-28 Eastman Chemical Company Multi-level tubular reactor with dual headers
US7868130B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Multi-level tubular reactor with vertically spaced segments
US7829653B2 (en) 2007-07-12 2010-11-09 Eastman Chemical Company Horizontal trayed reactor
US7868129B2 (en) 2007-07-12 2011-01-11 Eastman Chemical Company Sloped tubular reactor with spaced sequential trays
US7842777B2 (en) 2007-07-12 2010-11-30 Eastman Chemical Company Sloped tubular reactor with divided flow
US7834109B2 (en) * 2007-12-07 2010-11-16 Eastman Chemical Company System for producing low impurity polyester
CN101575409B (en) * 2008-05-07 2012-02-15 东丽纤维研究所（中国）有限公司 Preparation method of polybutylene terephthalate (PBT)
JP5330735B2 (en) * 2008-05-26 2013-10-30 三菱重工業株式会社 Method and apparatus for producing mono-lower alkyl monoalkanolamine
DE102008044440B4 (en) * 2008-08-18 2011-03-03 Lurgi Zimmer Gmbh Process and apparatus for the recovery of ethylene glycol in polyethylene terephthalate production
CN102239156B (en) * 2008-09-25 2014-10-15 塞格提斯有限公司 ketal ester derivatives
CN102459219A (en) 2009-06-22 2012-05-16 赛格提斯公司 Ketal compounds and uses thereof
CA2792018A1 (en) 2010-05-10 2011-11-17 Segetis, Inc. Fragrant formulations, methods of manufacture thereof and articles comprising the same
JP5567977B2 (en) * 2010-10-21 2014-08-06 株式会社日立製作所 Polytrimethylene terephthalate production apparatus and method, and acrolein removal apparatus
AU2013352172A1 (en) 2012-11-29 2015-06-11 Gfbiochemicals Limited Carboxy ester ketals, methods of manufacture, and uses thereof
JP6237129B2 (en) * 2012-11-29 2017-11-29 三菱ケミカル株式会社 Polyester manufacturing method
CN106220833A (en) * 2016-07-29 2016-12-14 中国石化仪征化纤有限责任公司 A kind of branched PBT copolyesters and preparation method thereof
CN107987265B (en) * 2016-10-27 2020-04-10 万华化学集团股份有限公司 Continuous preparation method of polyester polyol
CN114437331B (en) * 2022-02-07 2024-06-25 万华化学集团股份有限公司 Aliphatic polyester with oligomer residues and preparation method thereof

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878055A (en) 1970-06-04 1975-04-15 Ppg Industries Inc Reclamation of spent glycol by distillation in the presence of a catalytic amount of alkali metal hydroxide
DE2714898C3 (en) * 1977-04-02 1981-01-29 Basf Ag, 6700 Ludwigshafen Process for the continuous production of unsaturated polyesters
US4146729A (en) 1977-04-07 1979-03-27 E. I. Du Pont De Nemours And Company Process for preparing poly(ethylene terephthalate)
JPS5832897B2 (en) 1978-08-30 1983-07-15 松下電器産業株式会社 image display device
JPS5948058B2 (en) 1978-10-23 1984-11-24 東洋紡績株式会社 Continuous polyester manufacturing method
US5236558A (en) * 1982-09-23 1993-08-17 Allied-Signal Inc. Method to recycle spent ethylene glycol
JPS60163918A (en) * 1984-02-06 1985-08-26 Toyobo Co Ltd Continuous production of polyester
DE3544551C2 (en) 1985-12-17 2002-02-28 Zimmer Ag Process for the continuous production of high molecular weight polybutylene terephthalate
CN1054988A (en) * 1990-03-20 1991-10-02 中国石油化工总公司上海石油化工总厂 The method of polyester is produced in the direct esterification of no glycol recovering and refining
JPH0465426A (en) 1990-07-05 1992-03-02 Dainippon Ink & Chem Inc Production of polyester
KR950006718B1 (en) * 1991-12-13 1995-06-21 엘지전자주식회사 Method for producing polybutylenterepthalate
DE4306144A1 (en) * 1993-02-27 1994-09-01 Brown John Deutsche Eng Gmbh Process and polycondensation plant for the treatment of contaminated ethylene glycol
TW241359B (en) 1993-08-04 1995-02-21 Philips Electronics Nv
JPH07100734A (en) 1993-09-30 1995-04-18 Ando Electric Co Ltd Nc working machine
US5434239A (en) * 1993-10-18 1995-07-18 E. I. Du Pont De Nemours And Company Continuous polyester process
JPH09124783A (en) 1995-10-31 1997-05-13 Toray Ind Inc Production of polyester
JPH10279677A (en) * 1997-04-08 1998-10-20 Toray Ind Inc Production of polyester
TW482790B (en) * 1997-05-06 2002-04-11 Teijin Ltd Method for continuous production of polyester
JP3803198B2 (en) * 1997-09-10 2006-08-02 三井化学株式会社 Polyester production method
US5932105A (en) * 1997-10-01 1999-08-03 Mobile Process Technology, Co. Method of polyester manufacturing using crossflow membrane filtration

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WO2001083582A1 (en) 2001-11-08
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CN1383438A (en) 2002-12-04
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US20020161166A1 (en) 2002-10-31

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